CN101607924B - Preparation method of meta-alkyl urea series compounds - Google Patents
Preparation method of meta-alkyl urea series compounds Download PDFInfo
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- CN101607924B CN101607924B CN 200910090043 CN200910090043A CN101607924B CN 101607924 B CN101607924 B CN 101607924B CN 200910090043 CN200910090043 CN 200910090043 CN 200910090043 A CN200910090043 A CN 200910090043A CN 101607924 B CN101607924 B CN 101607924B
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Abstract
The invention relates to a preparation method of meta-alkyl urea series compounds. The meta-alkyl urea series compounds is prepared by adopting urea and primary amine or secondary amine of aliphatic or alicyclic in a synthesis reactor with a water-based reaction medium at 60-180 DEG C; wherein, the water-based reaction medium comprises a liquid which can provide protons, a metal which can perform complexation with amine and strengthen the nucleophilic attack of amine or a ion of the metal, and a nonionic surfactant or a quaternary ammonium salt surfactant; the pH value of the water-based reaction medium is 5-7; the metal or the ion thereof is at least one of Zn, Sc, Ti, Zr, V, Sn, Pb and Fe and the selected ion also comprises at least one of the following negative ions: OH-, Cl-, SO42-, NO3-, CO3-2, HCO3-, CH3COO- and C2H5COO- which can combine with the metal or the ion thereof. The method solves the problems of high demands for equipments, expensive raw material price, low synthesis yield and extremely expensive product price in the prior art, thus eliminating the obstruction in the industrial application of the product of the invention.
Description
Technical field
The present invention relates to a kind of compound method of organic cpds, particularly relate to a kind of fatty amine and urea reaction, method of the inclined to one side substituted type alkyl urea of catalytic preparation series compound in aqueous based systems passed through.
Background technology
Traditional nonionogenic tenside has good equilibrium surface tension performance, but the dynamic surface tension poor-performing; AS commonly used possesses good dynamic surface tension, but bubbles easily.
Substituted type alkyl urea series compound is one type of novel nonionic class tensio-active agent 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 researchs 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 are 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 in building-up process is high at present, expensive raw material price, and problem such as synthetic yield is low makes this product price extremely expensive, has limited its application in industry largely.
For inclined to one side substituted type carbamide derivative, early stage compound method is to utilize ammonia and phosgene verivate, 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 accomplished 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.The growing interest of Along with people's environmental pollution, for these reasons, the extremely application of verivate 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 substituted partially alkyl urea and can make with the alkali metal cyanate reaction by alkylamine and under sour environment in patent US-1785730.But this method is extremely dangerous in today, and prussic acid and verivate cyanate thereof are the hypertoxic compounds of generally acknowledging, can not in industrial production, be able to promote.The prepared product of this kind method is difficult to from reaction system, separate 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 has avoided the use of 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 HTHP; 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 like US-4310692, US-5099021.In these two pieces of patents, the author has mentioned and need under anhydrous condition, react, and has all introduced the notion of thinner, promptly reacts used medium.
In US-4310692, the author has proposed in the reaction kettle of closed environment through alkylamine (or ammonium salt) synthetic this compounds with the reaction higher yields of urea.In order to suppress serious side reaction, like the generation of biuret, need to add height and boil inert organic liquid as thinner, employed thinner comprises: chlorobenzene, dichlorobenzene, trichlorobenzene, toluene, YLENE etc.In US-5099021, the thinner of recommending to use then is N, and dinethylformamide, DMAC N,N, acetone, hexanaphthene and aromatic series halides wherein are advisable with chlorobenzene, and trichlorobenzene is best.
Owing to substituted type alkyl urea series compound is easy partially thermolysis taking place, so it is difficult unusually to remove the step of thinner in the last handling process, makes yield of product and purity all receive very big influence.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 industry go up this reaction of enforcement and becomes 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 ability.
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 yield of product and purity are lower; And the problems such as reaction conditions that need HTHP; 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 following:
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 of proton that can provide 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 practical implementation,
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 metals 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 through 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, like 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 it is active to have improved substrate, 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 according to the water-based reactions medium of different substrates and different proportionings to some extent, and generally the temperature with control remains 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.Generally speaking, 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 through drying under reduced pressure, realize the separation of product; For the subambient compound of fusing point, then need use method of extraction, through drying under reduced pressure, product is thoroughly separated then.
Generally speaking, in carbonyl nucleophilic addition(Adn)-elimination reaction, have the carbonyl of the substituted urea of alkyl bigger reactive behavior to be arranged, so this reaction process originally is difficult to realize on thermodynamics than no substituted (being urea); 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 can not ammonia in time be removed out reaction system the time, this reaction possibly 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 an 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 and be prone to decomposes a type 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 all to be prone to because of pressure difference inside and outside the reaction system chemical accident take place.
Comparatively speaking, reaction conditions of the present invention is gentle, and security is higher.
Embodiment
Embodiment 1
N, the N-diethyl urea is synthetic
In the four-hole bottle of the 1000mL that whisking appliance, TM 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 following: with 10g zinc-zinc oxide mixture, and 8g plumbous oxide-lead nitrate mixture, 2.5g diethylammonium ammonium chloride adds in the 250mL pure water successively, stirs and processes suspension-s, 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 accomplished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrating obtains pure article 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 whisking appliance, TM 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 following: with 10g zinc-zinc oxide mixture, and 10g red oxide of iron-iron(ic)chloride mixture, 1.5g dipropyl ammonium chloride adds in the 125mL pure water successively, stirs and processes suspension-s, 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 accomplished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrating obtains pure article 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 whisking appliance, TM 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 following: 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 processes suspension-s, 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 accomplished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrating obtains pure article 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 whisking appliance, TM 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 following: 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 processes suspension-s, 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 accomplished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrating 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 whisking appliance, TM 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 following: with 25g zinc-zinc acetate mixture, and 22g tin protochloride-lead nitrate mixture, 1g decyl ammonium chloride adds in the 63mL pure water successively; Suspension-s is processed 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 accomplished, reactor cooling was to room temperature, and crude product is isolated insolubles after thorough drying is filtered.Gained filtrating 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 YLENE as reaction medium, the volume of YLENE: the volume of diethylamine=2: 1, at 130 ℃ of reaction 20h down.After reaction finished, with a certain amount of YLENE 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 YLENE as reaction medium, the volume of YLENE: 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%.
Table 1 is seen in the reaction conditions of the foregoing description and Comparative Examples and effect data contrast
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 | YLENE | 1.0/2.0 | 0 | 130 | 20 | 39.1 |
| Comparative Examples 2 | 1.0/1.5 | YLENE | 1.0/3.0 | 0 | 130 | 25 | 37.1 |
Claims (7)
1. the preparation method of a 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 following:
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;
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 of proton that can provide is selected from least a and water in alcohol or the acid;
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, Sn, Pb and Fe;
Described water-based reactions medium also comprise can with following negatively charged ion that described metals ion combines at least a: OH
-, Cl
-, SO
4 2-, NO
3 -, CO
3 2-, HCO
3 -, CH
3COO
-And C
2H
5COO
-
In the described water-based reactions medium, by weight percentage, the water ratio is not less than 50%.
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 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.
3. 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 ℃.
4. 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.
5. 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.
6. 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.
7. 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 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 said 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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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US4310692A (en) * | 1979-09-14 | 1982-01-12 | Bayer Aktiengesellschaft | Process for the preparation of alkyl-ureas |
-
2009
- 2009-07-30 CN CN 200910090043 patent/CN101607924B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US4310692A (en) * | 1979-09-14 | 1982-01-12 | Bayer Aktiengesellschaft | Process for the preparation of alkyl-ureas |
Non-Patent Citations (2)
| Title |
|---|
| 张秀红等.N N-二烷基脲的合成及结构分析.《北京服装学院学报》.2006 |
| 张秀红等.N,N-二烷基脲的合成及结构分析.《北京服装学院学报》.2006,第26卷(第4期),第40-45页. * |
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