CN101607924A - A kind of method for preparing meta-alkyl urea series compounds - Google Patents
A kind of method for preparing meta-alkyl urea series compounds Download PDFInfo
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- CN101607924A CN101607924A CNA2009100900432A CN200910090043A CN101607924A CN 101607924 A CN101607924 A CN 101607924A CN A2009100900432 A CNA2009100900432 A CN A2009100900432A CN 200910090043 A CN200910090043 A CN 200910090043A CN 101607924 A CN101607924 A CN 101607924A
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- series compounds
- based reactions
- alkyl urea
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 112
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000004202 carbamide Substances 0.000 claims abstract description 35
- 150000001412 amines Chemical class 0.000 claims abstract description 32
- -1 alicyclic primary amine Chemical class 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 230000000536 complexating effect Effects 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 4
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 150000003335 secondary amines Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 235000013877 carbamide Nutrition 0.000 description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000012043 crude product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 150000003672 ureas Chemical class 0.000 description 5
- 150000003973 alkyl amines Chemical class 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- PCKKNFLLFBDNPA-UHFFFAOYSA-N 1,1-dibutylurea Chemical compound CCCCN(C(N)=O)CCCC PCKKNFLLFBDNPA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical class ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- WSUTUEIGSOWBJO-UHFFFAOYSA-N dizinc oxygen(2-) Chemical compound [O-2].[O-2].[Zn+2].[Zn+2] WSUTUEIGSOWBJO-UHFFFAOYSA-N 0.000 description 2
- PIFBJINVDJJYCV-UHFFFAOYSA-J dizinc tetraacetate Chemical compound [Zn+2].[Zn+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O PIFBJINVDJJYCV-UHFFFAOYSA-J 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 description 1
- IRGIISRSKQVGJH-UHFFFAOYSA-N 1,1-dipentylurea Chemical compound CCCCCN(C(N)=O)CCCCC IRGIISRSKQVGJH-UHFFFAOYSA-N 0.000 description 1
- KTKDYVVUGTXLJK-UHFFFAOYSA-N 1,1-dipropylurea Chemical compound CCCN(C(N)=O)CCC KTKDYVVUGTXLJK-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IMQDYOVRUGGNNV-UHFFFAOYSA-M C(C)(=O)[O-].[Zn+2].[O-2].[Zn+2].[Zn+2] Chemical compound C(C)(=O)[O-].[Zn+2].[O-2].[Zn+2].[Zn+2] IMQDYOVRUGGNNV-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-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
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 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
- 238000004440 column chromatography Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- RMKNCYHVESPYFD-UHFFFAOYSA-N decan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCC[NH3+] RMKNCYHVESPYFD-UHFFFAOYSA-N 0.000 description 1
- HHCZYYBKCPWBMS-UHFFFAOYSA-N decylurea Chemical compound CCCCCCCCCCNC(N)=O HHCZYYBKCPWBMS-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HDITUCONWLWUJR-UHFFFAOYSA-N diethylazanium;chloride Chemical compound [Cl-].CC[NH2+]CC HDITUCONWLWUJR-UHFFFAOYSA-N 0.000 description 1
- XVEUERTYUNCPOM-UHFFFAOYSA-N dipentylazanium;chloride Chemical compound Cl.CCCCCNCCCCC XVEUERTYUNCPOM-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000001508 eye Anatomy 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- ODYNBECIRXXOGG-UHFFFAOYSA-N n-butylbutan-1-amine;hydron;chloride Chemical compound [Cl-].CCCC[NH2+]CCCC ODYNBECIRXXOGG-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- GAZIBGHLWYHBDT-UHFFFAOYSA-N n-propylpropan-1-amine;hydrochloride Chemical compound Cl.CCCNCCC GAZIBGHLWYHBDT-UHFFFAOYSA-N 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001149 thermolysis 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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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Abstract
The present invention is a kind of method for preparing meta-alkyl urea series compounds.Described meta-alkyl urea series compounds makes at 60～180 ℃ in the synthesis reactor of water-based reactions medium with urea and aliphatics or alicyclic primary amine or secondary amine.Wherein the water-based reactions medium comprise liquid that proton can be provided and can with the amine complexing, and strengthen metal or its ion of its nucleophilic attack ability, and non-ionic type or quaternary ammonium salt cationic surfactant are formed; The pH value of water-based reactions medium is 5～7; Described metal or its ion are selected from least a of Zn, Sc, Ti, Zr, V, Sn, Pb, Fe, and are selected from can combine with described metal ion following anionic at least a: OH
-, Cl
-, SO
4 2-, NO
3 -, CO
3 2-, HCO
3 -, CH
3COO
-And C
2H
5COO
-This method has solved prior art ubiquity equipment requirements height, and the problem that expensive raw material price, the low and product price of synthetic yield are extremely expensive has been cleared away the obstacle of the industrial application of this product.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, particularly relate to a kind of by fatty amine and urea reaction, the method for the inclined to one side substituted type alkyl urea of catalytic preparation series compound in aqueous based systems.
Background technology
Traditional nonionogenic tenside has good equilibrium surface tension performance, but the dynamic surface tension poor-performing; Anion surfactant commonly used possesses good dynamic surface tension, but bubbles easily.
Substituted type alkyl urea series compound is the novel nonionic class tensio-active agent of a class partially.Since the eighties of last century the nineties, substituted type alkyl urea series compound has caused people's extensive concern in the excellent results aspect reduction balance and the dynamic surface tension partially.A large amount of studies show that, substituted type alkyl urea series compound not only can provide good balance and dynamic surface tension character partially, and is low foaming; In addition, this compounds also has characteristics such as of light color and smell is little, thus the every field of being widely used in.
Substituted type alkyl urea series compound often is applied to fields such as various low-sudsing detergent, coating, printing ink, papermaking partially.And this compounds also is widely used in field of textiles, as: wet-spinning, dyeing keratin-fiber, fiber fermentation, grey cloth kiering etc.; In addition, this compounds also can be used for tackiness agent, agricultural formulating, photoresist development and field of medicaments.In US-5985968 one literary composition, how the author just utilizes the surface tension of inclined to one side substituted type alkyl urea compounds reduction aqueous based systems, and Application Areas has been done extremely detailed argumentation.
But, this product ubiquity equipment requirements height in building-up process at present, expensive raw material price, problem such as synthetic yield is low makes this product price extremely expensive, has limited it largely in industrial application.
For inclined to one side substituted type carbamide derivative, early stage synthetic method is to utilize ammonia and phosgene derivative, and reaction, productive rate is very high, can reach more than 90%---such as the amido formyl chloride---.But simultaneously, this reaction process is again unmanageable, because very exothermic, reaction almost can be finished moment, very easily blasts.Owing to have hydrochloric acid to generate in the by product, therefore the rotproofness of conversion unit had relatively high expectations.In addition, the acyl chloride compound has the intense stimulus effect to eyes, mucous membrane, respiratory tract and skin in the raw material, belongs to high carcinogenic substance.Along with the growing interest of people's environmental pollution, for these reasons, the extremely application of derivative in building-up reactions of phosgene more and more obtains restriction, a lot of countries all strictness limit such reaction.
As far back as nineteen twenty-nine, Tenney L.Davis and Kenneth C.Blanchard have just proposed inclined to one side replacement in patent US-1785730 alkyl urea can make with the alkali metal cyanate reaction by alkylamine and under sour environment.But this method is extremely dangerous in today, and prussic acid and derivative cyanate thereof are the hypertoxic compounds of generally acknowledging, can not be promoted in industrial production.The prepared product of this kind method is difficult to separate from reaction system simultaneously, and purification difficult, output are very low.
The method of the inclined to one side substituted type alkyl urea series compound of another kind of preparation is to utilize urea and suitable alkylamine, and this method avoids having used highly toxic reaction raw materials, commercial more suitable.The US-3937727 reported first this kind method, success has synthesized N, N-dimethyl urea under the reaction conditions of High Temperature High Pressure; Patent points out that also such reaction must take place in the reaction system of over dry simultaneously, and the introducing of water can cause competing reaction, causes intermediate product to decompose, and takes place thereby suppressed reaction.Similar afterwards patent has all been followed this principle as US-4310692, US-5099021.In these two pieces of patents, the author has mentioned and need react under anhydrous condition, and has all introduced the notion of thinner, promptly reacts used medium.
In US-4310692, the author has proposed in the reactor of closed environment by alkylamine (or ammonium salt) synthetic this compounds with the reaction higher yields of urea.In order to suppress serious side reaction, as the generation of biuret, need to add height and boil inert organic liquid as thinner, employed thinner comprises: chlorobenzene, dichlorobenzene, trichlorine benzene,toluene,xylene etc.In US-5099021, the thinner of recommending to use then is N, and dinethylformamide, N,N-dimethylacetamide, acetone, hexanaphthene and aromatic series halides wherein are advisable with chlorobenzene, trichlorobenzene the best.
Because thermolysis easily takes place substituted type alkyl urea series compound partially,, make the productive rate of product and purity all be subjected to very big influence so it is difficult unusually to remove the step of thinner in the last handling process.The theoretical yield that the author infers about 80%, but in the actually operating, the loss in the deduction aftertreatment, its actual constant has only 60～70%, even lower.This reaction also need be accomplished by autoclave in addition, makes this reaction of industrial enforcement become difficult.
Summary of the invention
The contriver of present patent application finds under study for action, not only the introducing of an amount of water can not influence the generation of reaction, catalyzing urea and alkylamine react to a certain extent on the contrary.Water is a kind of extremely cheap solvent, and its process of removing also is easy to the more effective reduction reaction cost of energy.
Serious for solving the side reaction that prior art exists, and make that owing to the step of removing solvent in the last handling process is difficult unusually the productive rate of product and purity are lower, and the problems such as reaction conditions that need High Temperature High Pressure, the method that the invention provides an economy and very easily implement has made highly purified inclined to one side substituted type alkyl urea series compound with high yield.
The preparation method of a kind of meta-alkyl urea series compounds of the present invention is achieved in that
Described meta-alkyl urea series compounds is that raw material makes in synthesis reactor with urea and aliphatics or alicyclic primary amine or secondary amine; Described preparation general formula is as follows:
The alkyl or cycloalkyl of R=H or C1～C12 wherein, the alkyl or cycloalkyl of R '=C1～C12;
Described chemosynthesis reaction has the katalysis reaction medium---carries out in the water-based reactions medium;
Described water-based reactions medium is a kind of mixture, comprises the liquid that proton can be provided and metal or its ion that can improve its nucleophilic attack ability with the amine complexing;
The described liquid that proton can be provided is selected from least a and water in alcohol or the acid;
Described metal or its ion are selected from down at least a in the column element: the metallic element of IIB, IIIB, IVB, VB, IVA and the 8th family.
In concrete enforcement,
The pH value of described water-based reactions medium is 5～7;
Described metal or its ion are selected from down at least a in the column element: Zn, Sc, Ti, Zr, V, Sn, Pb and Fe;
Described water-based reactions medium also comprise can with following negatively charged ion that described metal ion combines at least a: OH
-, Cl
-, SO
4 2-, NO
3 -, CO
3 2-, HCO
3 -, CH
3COO
-And C
2H
5COO
-
This is owing to by the oxygen on the protonated urea carbonyl, can improve the reactive behavior of its carbonyl, makes it to be easy to take place nucleophilic substitution reaction; The existence of water can suppress urea generation biuret teaction simultaneously.Using the proton type solvent in this process, can be all liquid that proton can be provided, as water, alcohols, acids, or its mixture.In addition some specific metal or its ion can with the amine complexing, improve the ability of its nucleophilic attack, such as Ti, V, Sc, Zr, Zn, Sn, Pb, Fe etc. or its compound.By this principle, the water-based reactions medium of the specified proportion of preparation has the ability of catalyzing urea generation aminolysis reaction;
In the described water-based reactions medium, by weight percentage, water is more than or equal to 50%, and all the other substances content are less than or equal to 5%;
The mol ratio of described urea and amine is 1～3: 1; Can determine according to the activity of amine in the actually operating.As a rule, active higher amine can suitably reduce the consumption of urea, and vice versa;
The volume ratio of described amine and water-based reactions medium is 1～5: 1, and this also is to determine according to the activity of amine, and generally speaking, the activity of amine is high more, and the consumption of water-based reactions medium is few more;
Above-mentioned described water-based reactions medium can also comprise emulsifying dispersant; Described emulsifying dispersant is selected from non-ionic type or quaternary ammonium salt cationic surfactant, and its add-on is no more than 1% of water-based reactions medium by weight percentage, so more helps the dispersion of metal and amine.Can be with urea and amine solvent, disperse or be suspended in this water-based reactions medium, the proton in the system can combine with the oxygen on the urea carbonyl, metal or its positively charged ion then with amine generation complexing, thereby improved the substrate activity, catalysis reaction take place;
It is good that synthesis reaction temperature is 60～180 ℃.The beginning of urea and amine reaction need provide energy so that reaction activity to be provided.After the reaction beginning, entire reaction is an endothermic process, therefore needs to continue heating.The control of its temperature of reaction should change to some extent according to the water-based reactions medium of different substrates and different proportionings, generally the temperature of controlling is remained on 5～10 ℃ under the reaction mixture boiling point;
Described synthesising reacting time is 10～60 hours.This is mainly by temperature of reaction and the active decision of substrate length.In general, more SA amine needs the long reaction times; But if suitable rising temperature of reaction can shorten the reaction times.
Described meta-alkyl urea series compounds product is cooled to room temperature, and behind the dry filter, product can be purified with recrystallization or method of extraction.In product separates purification process, be higher than the product of room temperature for fusing point, can use the method for recrystallization, then by drying under reduced pressure, realize the separation of product; For the subambient compound of fusing point, then need to use method of extraction, by drying under reduced pressure, product is thoroughly separated then.
In general, in carbonyl nucleophilic addition(Adn)-elimination reaction, have the carbonyl of the urea of alkyl replacement bigger reactive behavior not to be arranged, so this reaction process originally is difficult to realize on thermodynamics than there being (being urea) that replace; But according to principle of dynamics, reaction is in case take place, and after being substituted the ammonia that gets off and being discharged from reaction system with gaseous form, reaction process will be irreversible, thereby promote reaction to carry out.Therefore, if ammonia in time can not be removed out reaction system the time, this reaction may take place hardly; Have only after the ammonia that generates in time is moved out of reaction system, reaction could continue that also end reaction is complete.In the operating process of reality, can take to increase an ammonia absorption unit, to realize this purpose.
Be compared to the method that prior art US-3937727, US-4310692 and US-5099021 introduce, of the present inventionly obviously have the following advantages:
1. the present invention does not have side reaction.The aforesaid method of prior art all uses high boiling inert liq as thinner in the over dry condition, and under this kind reaction conditions, condensation reaction very easily takes place urea, generates biuret, and this side reaction can have a strong impact on output along with temperature rising and constantly aggravation.
The present invention uses aqueous based systems, and under this kind condition, the condensation reaction of urea has obtained great inhibition, has guaranteed output, and degree of purity of production.
2. the present invention has simplified post-processing step.Aforesaid method has all used height to boil liquid as thinner, in removing the process of desolvating, because the product that generates is the compound that is soluble in organic liquid, thereby can only adopts the distillatory method to remove and desolvate.But carbamide compounds is easy decomposition class material, and the decomposition point of most carbamide compounds even be lower than its fusing point so must take the method for underpressure distillation, is controlled at distillation temperature below the decomposition point of product, has increased technology difficulty greatly.
Solvent of the present invention is a water, and the content of aqueous phase solvent is a small amount of, and product solubleness therein is limited, can utilize the method for extraction or recrystallization that it is separated, and has simplified last handling process.
3. the present invention is with low cost.Aforesaid method will use the reaction under high pressure system, and uses the height organic liquid that boils.
The present invention can use in condition of normal pressure, and the main body of reaction medium is water, has reduced reaction cost.
4. the present invention has reduced the danger of reaction.Aforesaid method will use reaction under high pressure system and underpressure distillation operation that chemical accident all easily takes place because of pressure inside and outside the reaction system is different.
Comparatively speaking, reaction conditions gentleness of the present invention, security is higher.
Embodiment
Embodiment 1
N, the N-diethyl urea is synthetic
In the four-hole bottle of the 1000mL that agitator, thermometer and reflux are housed, add 175g urea, the 250mL diethylamine, the mol ratio of urea and amine is 1.2: 1.0; 250mL water-based reactions medium, the volume ratio of amine and water-based reactions medium is 1: 1.The compound method of this water-based reactions medium is as follows: with 10g zinc-zinc oxide mixture, and 8g plumbous oxide-lead nitrate mixture, 2.5g diethyl ammonium chloride adds in the 250mL pure water successively, stirs and makes suspension, and its pH value is between 6～7.
Reaction system is stirred, is heated to 60 ℃, and the ammonia that overflows is absorbed by acid through device for absorbing tail gas.Behind the 60h, reaction finishes.
After reaction was finished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrate obtains pure product through recrystallization, is white needle-like crystals.Productive rate 83.3%, 68.1～68.9 ℃ of fusing points.
Embodiment 2
N, N-dipropyl urea is synthetic
In the four-hole bottle of the 1000mL that agitator, thermometer and reflux are housed, add 165g urea, the 250mL dipropyl amine, the mol ratio of urea and amine is 1.5: 1.0; 125mL water-based reactions medium, the volume ratio of amine and water-based reactions medium is 2: 1.The compound method of this water-based reactions medium is as follows: with 10g zinc-zinc oxide mixture, and 10g ferric oxide-iron(ic) chloride mixture, 1.5g dipropyl ammonium chloride adds in the 125mL pure water successively, stirs and makes suspension, and its pH value is between 6～7.
Reaction system is stirred, is heated to 90 ℃, and the ammonia that overflows is absorbed by acid through device for absorbing tail gas.Behind the 35h, reaction finishes.
After reaction was finished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrate obtains pure product through recrystallization, is white needle-like crystals.Productive rate 81.9%, 47.8～48.9 ℃ of fusing points.
Embodiment 3
N, N-dibutyl urea is synthetic
In the four-hole bottle of the 1000mL that agitator, thermometer and reflux are housed, add 135g urea, the 250mL dibutylamine, the mol ratio of urea and amine is 1.5: 1.0; 100mL water-based reactions medium, the volume ratio of amine and water-based reactions medium is 2.5: 1.The compound method of this water-based reactions medium is as follows: with 17g zinc-zinc oxide-zinc acetate mixture, and the 15g tin protochloride, 1g dibutyl ammonium chloride adds in the 100mL pure water successively, stirs and makes suspension, and its pH value is between 6～7.
Reaction system is stirred, is heated to 120 ℃, and the ammonia that overflows is absorbed by acid through device for absorbing tail gas.Behind the 24h, reaction finishes.
After reaction was finished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrate obtains pure product through recrystallization, is white needle-like crystals.Productive rate 81%, 26.6～28.4 ℃ of fusing points.
Embodiment 4
N, N-diamyl urea is synthetic
In the four-hole bottle of the 1000mL that agitator, thermometer and reflux are housed, add 149g urea, the 250mL diamylamine, the mol ratio of urea and amine is 2.0: 1.0; 85mL water-based reactions medium, the volume ratio of amine and water-based reactions medium is 3.0: 1.0.The compound method of this water-based reactions medium is as follows: with 25g zinc-zinc acetate mixture, and 22g tin protochloride-lead nitrate mixture, 1.5g diamyl ammonium chloride adds in the 85mL pure water successively, stirs and makes suspension, and its pH value is between 6～7.
Reaction system is stirred, is heated to 140 ℃, and the ammonia that overflows is absorbed by acid through device for absorbing tail gas.Behind the 15h, reaction finishes.
After reaction was finished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrate obtains colourless liquid through extraction, drying under reduced pressure.Productive rate 84%.
Embodiment 5
N-decyl urea is synthetic
In the four-hole bottle of the 1000mL that agitator, thermometer and reflux are housed, add 187.5g urea, the 250mL n-Decylamine, the mol ratio of urea and amine is 2.5: 1.0; 63mL water-based reactions medium, the volume ratio of amine and water-based reactions medium is 4.0: 1.0, the compound method of this water-based reactions medium is as follows: with 25g zinc-zinc acetate mixture, 22g tin protochloride-lead nitrate mixture, 1g decyl ammonium chloride adds in the 63mL pure water successively, suspension is made in stirring, and its pH value is between 6～7.
Reaction system is stirred, is heated to 160 ℃, and the ammonia that overflows is absorbed by acid through device for absorbing tail gas.Behind the 15h, reaction finishes.
After reaction was finished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrate obtains colourless liquid through extraction, drying under reduced pressure.Productive rate 82.4%.
Comparative Examples 1
N, the N-diethyl urea is synthetic
Zhang Xiuhong utilizes the US-4310692 reported method in " N, the synthetic and structural analysis of N-dialkyl ureas " literary composition, synthesized N, the N-diethyl urea.Concrete reaction conditions is: the diethylamine amount of substance: urea amount of substance=2.5: 1, with dimethylbenzene as reaction medium, the volume of dimethylbenzene: the volume of diethylamine=2: 1, at 130 ℃ of reaction 20h down.After reaction finished, with a certain amount of dimethylbenzene washing crude product, freeze-day with constant temperature got off-white powder shape solid.Productive rate 39.1%, product fusing point are 62.5～65.9 ℃.
Comparative Examples 2
N, N-dibutyl urea is synthetic
Zhang Xiuhong utilizes the US-4310692 reported method in " N, the synthetic and structural analysis of N-dialkyl ureas " literary composition, synthesized N, N-dibutyl urea.Concrete reaction conditions is: the dibutylamine amount of substance: urea amount of substance=1.5: 1, with dimethylbenzene as reaction medium, the volume of dimethylbenzene: the volume of diethylamine=3: 1, at 130 ℃ of reaction 25h down.After reaction finished, with the column chromatography separated product, freeze-day with constant temperature obtained colourless oil liquid.Productive rate 37.1%.
The reaction conditions of the foregoing description and Comparative Examples and effect data contrast see Table 1
Table 1
| Embodiment number | Urea/amine (mol ratio) | Used thinner | Amine/thinner (volume ratio) | The moisture ratio of thinner (%) | Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) |
| ??1 | ??1.2/1.0 | Water-based mixture | ??1.0/1.0 | ??92 | ??60 | ??60 | ??83.3 |
| ??2 | ??1.5/1.0 | Water-based mixture | ??2.0/1.0 | ??85 | ??90 | ??35 | ??81.9 |
| ??3 | ??1.5/1.0 | Water-based mixture | ??2.5/1.0 | ??75 | ??120 | ??24 | ??81.0 |
| ??4 | ??2.0/1.0 | Water-based mixture | ??3.0/1.0 | ??63 | ??140 | ??15 | ??84.0 |
| ??5 | ??2.5/1.0 | Water-based mixture | ??4.0/1.0 | ??57 | ??160 | ??15 | ??82.4 |
| Comparative Examples 1 | ??1.0/2.5 | Dimethylbenzene | ??1.0/2.0 | ??0 | ??130 | ??20 | ??39.1 |
| Comparative Examples 2 | ??1.0/1.5 | Dimethylbenzene | ??1.0/3.0 | ??0 | ??130 | ??25 | ??37.1 |
Claims (10)
- The preparation method of 1 one kinds of meta-alkyl urea series compounds is characterized in that:Described meta-alkyl urea series compounds is that raw material makes in synthesis reactor with urea and aliphatics or alicyclic primary amine or secondary amine; The preparation general formula of described meta-alkyl urea series compounds is as follows:The alkyl or cycloalkyl of R=H or C1～C12 wherein, the alkyl or cycloalkyl of R '=C1～C12;Described chemosynthesis reaction carries out in having the water-based reactions medium of katalysis.
- 2. according to the preparation method of the meta-alkyl urea series compounds of claim 1, it is characterized in that:Described water-based reactions medium is a kind of mixture, comprises the liquid that proton can be provided and metal or its ion that can improve its nucleophilic attack ability with the amine complexing;The described liquid that proton can be provided is selected from least a and water in alcohol or the acid;Described metal or its ion are selected from down at least a in the column element: the metallic element of IIB, IIIB, IVB, VB, IVA and the 8th family.
- 3. according to the preparation method of the meta-alkyl urea series compounds of claim 2, it is characterized in that:The pH value of described water-based reactions medium is 5～7;Described metal or its ion are selected from down at least a in the column element: Zn, Sc, Ti, Zr, V, Sn, Pb and Fe;Described water-based reactions medium also comprise can with following negatively charged ion that described metal ion combines at least a: OH -, Cl -, SO 4 2-, NO 3 -, CO 3 2-, HCO 3 -, CH 3COO -And C 2H 5COO -
- 4. according to the preparation method of the meta-alkyl urea series compounds of claim 2, it is characterized in that:In the described water-based reactions medium, by weight percentage, the water ratio is not less than 50%.
- 5. according to the preparation method of the meta-alkyl urea series compounds of claim 2, it is characterized in that:Described water-based reactions medium also comprises emulsifying dispersant, and described emulsifying dispersant is selected from non-ionic type or quaternary ammonium salt cationic surfactant, and its add-on is no more than 1% of water-based reactions medium by weight percentage.
- 6. according to the preparation method of the meta-alkyl urea series compounds of claim 1, it is characterized in that:Described synthesis reaction temperature is 60～180 ℃.
- 7. according to the preparation method of the meta-alkyl urea series compounds of claim 1, it is characterized in that:The mol ratio of described urea and amine is 1～3: 1;The volume ratio of described amine and water-based reactions medium is 1～5: 1.
- 8. according to the preparation method of the meta-alkyl urea series compounds of claim 1, it is characterized in that:Described synthesising reacting time is 10～60 hours.
- 9. according to the preparation method of the meta-alkyl urea series compounds of claim 1, it is characterized in that:Described meta-alkyl urea series compounds product is cooled to room temperature, behind the dry filter, purifies with recrystallization or extracting process.
- 10. according to the preparation method of the meta-alkyl urea series compounds of claim 3, it is characterized in that:In the described water-based reactions medium, by weight percentage, the water ratio is not less than 50%;Described water-based reactions medium also comprises emulsifying dispersant, and described emulsifying dispersant is selected from non-ionic type or quaternary ammonium salt cationic surfactant, and its add-on is no more than 1% of water-based reactions medium by weight percentage;Described synthesis reaction temperature is 60～180 ℃;The mol ratio of described urea and amine is 1～3: 1;The volume ratio of described amine and water-based reactions medium is 1～5: 1;Described synthesising reacting time is 10～60 hours;Described meta-alkyl urea series compounds product is cooled to room temperature, behind the dry filter, purifies with recrystallization or extracting process.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US1785730A (en) * | 1927-11-05 | 1930-12-23 | Tenney L Davis | Di-alkyl urea |
| DE855551C (en) * | 1942-05-13 | 1952-11-13 | Knoll Ag | Process for the production of mono- or symmetrical dimethyl urea |
| US3937727A (en) * | 1974-07-05 | 1976-02-10 | Ashland Oil, Inc. | Process for preparing n, n-dimethylurea |
| DE2937331A1 (en) * | 1979-09-14 | 1981-04-02 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING ALKYL UREAS |
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