CN102617476A - Method for synthesizing allantoin - Google Patents
Method for synthesizing allantoin Download PDFInfo
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- CN102617476A CN102617476A CN2012100609650A CN201210060965A CN102617476A CN 102617476 A CN102617476 A CN 102617476A CN 2012100609650 A CN2012100609650 A CN 2012100609650A CN 201210060965 A CN201210060965 A CN 201210060965A CN 102617476 A CN102617476 A CN 102617476A
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- KIWPHAHPNLTBJR-UHFFFAOYSA-N CCC(C)CCC(CC)N Chemical compound CCC(C)CCC(CC)N KIWPHAHPNLTBJR-UHFFFAOYSA-N 0.000 description 1
- PRMPZAXGIXCYPW-UHFFFAOYSA-N CCC(C)N(C(C)C)C(C)(C)C Chemical compound CCC(C)N(C(C)C)C(C)(C)C PRMPZAXGIXCYPW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for synthesizing allantoin. The allantoin is synthesized by taking acid ionic liquid as a catalyst and glyoxylic acid and urea as raw materials. A process is simple, raw materials are bulk chemical raw materials, yield is high, the method is easy to industrially popularize, the yield of allantoin is stable and can reach over 68 percent, and the acid ionic liquid used as the catalyst can be repeatedly used for more than 5 times; and the process is pollution-free and environment-friendly, and has a good ecological effect and social and economic benefits. Through assay determination, the content of the obtained allantoin product is in the range required by the United States Pharmacopeia (USP29), and other indexes of the obtained allantoin product also meet the USP 29.
Description
Technical field
The present invention relates to a kind of method of synthetic allantoin.
Background technology
Wallantoin (allantoin), chemical name are imidazole alkane-2 between the 1-urea groups, and the 4-diketone belongs to the imidazoles heterogeneous ring compound, and there is odorless, tasteless in crystal or the crystalline form form of powder with white usually.
Wallantoin extensively is present in nature, in allantoic fluid, fetus urine, human body and mammiferous embryo and movement, also contains wallantoin in tobacco, wheat, the beet.But natural wallantoin limited amount, extraction process is complicated, and productive rate is extremely low, so mostly current commodity wallantoin is synthetic.
Pharmaceutically, wallantoin is the medicine with multiple function, and it both can directly use; Also can do additive; Wallantoin can be cured various tetter, like psoriatic, dermatitis, xerosis cutis etc., can promote skin cells and tissue growth, promote wound effect such as healing and analgesia rapidly; Skin or organized renewing true colours can be made, various ulcers can be treated.On daily-use chemical industry; Wallantoin at home and abroad use still do not have so far stimulate, the report of photosensitive, anaphylaxis and other toxic side effect; Can have skin moisten directly as the additive (like cream frost, emulsion etc.) of the cosmetics of super quality and the additive (like toothpaste, shampoo, soap etc.) of other daily chemicals, preserve moisture, effect such as cutin softening and promotion cell regeneration.In addition, wallantoin is a plant growth regulators, and the wallantoin of trace is used in growth that can stimulating plant, can make wheat, citrus, paddy rice, vegetables and soybean yield-increasing, and have solid fruit, effect such as accelerate the ripening.Wallantoin is again the various composite fertilizers of exploitation, little fertilizer, long-acting fertilizer or the requisite raw material of fertilizer such as slow released fertilizer and rare-earth fertilizer, on agricultural, has important use.Wallantoin has the cell proliferation of promoting digestion road simultaneously, strengthens Normocellular vigor, improves the effect of pipe intestinal digesting absorptive function, can make livestock and poultry that popular eqpidemic disease is produced resistibility simultaneously, also is a kind of good fodder additives.Because the widespread use of wallantoin, demand increases year by year, study a kind of efficiently, the wallantoin synthesis technique of high yield, environmental protection is significant.
At present, the compound method of wallantoin is many to be that raw material is synthetic with oxoethanoic acid and urea, but productive rate does not all surpass 70%.It is that the productive rate of catalyzer synthetic allantoin is 59.3% that Li Guiyun, Ma Jiangquan disclose in " wallantoin synthetic and characterize " (" Jiangsu Petrochemical Engineering College journal ") with nitric acid, sulfuric acid nitration mixture; Its raw material oxoethanoic acid is produced with nitric acid oxidation method; Do not pass through purifying with regard to the direct production wallantoin, product can receive influence and the downgrade of the by product that residual oxalic dialdehyde and by product oxalic acid and multiple reaction produce.It is that the productive rate of catalyzer synthetic allantoin is between 52%～58% that Lei Hong etc. disclose in " wallantoin production technique and Market Summary " (" the 21st technical conferences collection of thesis of nitrogen information cooperative groups in the whole nation ") with mineral acids such as sulfuric acid, hydrochloric acid and nitric acid; Chinese patent publication number CN1528749A, in open day on September 15th, 2004, invention and created name is " novel allantoin synthesis process ", this application case discloses with metal catalyst catalysis synthetic allantoin yield only can reach 56%.In addition, they be that the report of catalyzer synthetic allantoin is also of common occurrence with the solid acid, but productive rate is many below 60%, only history peak etc. in " novel allantoin synthesis process " (" detergents and cosmetic technology ") with phosphorus heteropoly tungstic acid [H
3PW
12O
40X H
2O] be catalyzer, productive rate can reach 68.6%, but amount of urea is too much; Pay firewood water chestnut etc. at " SO in 2007
4 2-/ TiO
2The solid superacid as catalyst synthetic allantoin " in (" the 11st catalysis academic conference ") with SO
4 2-/ TiO
2To be that catalyst synthetic allantoin productive rate is the highest also only reach 57.35% to solid super-strong acid, and solid acid makes difficulty, and cost is high, is not suitable for suitability for industrialized production.In addition; Chinese patent publication number CN1765888A; In open day on May 3rd, 2006, invention and created name is " a kind of synthesis technique of wallantoin ", and it is that catalysis synthetic allantoin yield can arrive 69.6% that this application case discloses with gel-type strongly acidic cation exchange resin or macroporous type strongly acidic cationic exchange resin; But catalyzer needs to handle, and production cost is high.
The compound method of prior art wallantoin has: (1) uric acid potassium permanganate oxidation method, this method are used potassium permanganate as oxygenant, and reaction belongs to strong oxidizing reaction, and is wayward, be not suitable for scale operation, and uric acid cost height is difficult to obtain; (2) oxoethanoic acid calcium salt acid-soluble method, this method is carried out in two steps, and preparation oxoethanoic acid calcium generates wallantoin with hcl acidifying and urea condensation more earlier, and this method needs strong acid and strong base in reaction process, not easy to operate, and productive rate is low, is not suitable for scale operation; (3) urea dichloro acetic acid heating method, this one step of method generates wallantoin, but reaction needed methyl alcohol is as solvent; And need 40 ℃～50 ℃ of heating, make reaction process have explosion hazard, and this reaction needed underpressure distillation; Complicated operation, and productive rate is low, is not suitable for scale operation; (4) urea oxoethanoic acid condensation method; This method is the method that current wallantoin manufacturer generally adopts; This method is through one step of allantois and oxoethanoic acid condensation production wallantoin, and the mixing acid of using strong acid such as traditional protonic acid such as sulfuric acid, phosphoric acid, hydrochloric acid and different ratios protonic acid can obtain the higher productive rate of relative productive rate as catalyzer, and has simple to operate; Raw material is easy to get; The relative advantage of higher of productive rate, acid high but these routes also exist synthesis mother liquid, the problem of three wastes difficult treatment.
Ionic liquid (Ionic Liquids) is the focus of studying in the chemical field in recent years, is considered to and supercritical CO
2Constitute three big green solvent and catalytic medias together with double water-phase, have broad application prospects.The present invention uses
acidic ion liquid as the Preparation of Catalyst wallantoin; This is to be that Preparation of Catalyst obtains high yield, high-quality product with the ionic liquid for the first time; On basis, invented novel a, friendly process efficiently through research and development constantly.
Summary of the invention
The object of the invention provides a kind of compound method of wallantoin.
The compound method of said wallantoin; With
acidic ion liquid is catalyzer, is the raw material synthetic allantoin with oxoethanoic acid and urea.
Specifically, the compound method of said wallantoin comprises: in reactor drum, add aqueous glyoxylic acid, urea and catalyzer, stir, heating; Behind reaction 4.0～24.0h, reaction mixture is cooled to room temperature (15 ℃～25 ℃), filters, wash, oven dry obtains finished product; To filtrate and washing lotion merges collection and treatment and obtains catalyzer, repeat catalysis next time.
The mass concentration of said aqueous glyoxylic acid is preferably 20%～80%, and more preferably the mass concentration of aqueous glyoxylic acid is 20%～60%; The mass concentration of better preferred aqueous glyoxylic acid is 40%～50%; Wherein, oxalic dialdehyde and the oxalic acid content (weight ratio) in the preferred aqueous glyoxylic acid is not higher than 1.0%, 3.0% respectively.
Said Heating temperature is preferably 40 ℃～80 ℃, and more preferably Heating temperature is 60 ℃～70 ℃; Better preferred Heating temperature is 66 ℃～68 ℃.
The mol ratio of said oxoethanoic acid and urea is preferably 1: 2.0～and 1: 4.5, more preferably the mol ratio of oxoethanoic acid and urea is 1: 3.5～1: 4.5; The mol ratio of better preferred oxoethanoic acid and urea is 1: 3.8～1: 4.3; The mol ratio of best preferred oxoethanoic acid and urea is 1: 4.0～1: 4.3.
The mol ratio of said oxoethanoic acid and catalyzer is preferably 1: 0.2～and 1: 0.5, more preferably the mol ratio of oxoethanoic acid and catalyzer is 1: 0.3～1: 0.4;
Said washing stirs (about 20～60min) for filter cake being placed the water of 2～4 times of weight; Can wash repeatedly in case of necessity;
The described reaction times is generally 4.0～24.0h, and the preferred reaction time is 5.0～12.0h, and more preferably the reaction times is 5.5～7.0h.
Described oven dry generally can be heating, drying (like baking oven), and temperature is 60 ℃～150 ℃, and preferred bake out temperature is 80 ℃～110 ℃, and best bake out temperature is 95 ℃～105 ℃.
Said catalyzer is
acidic ion liquid;
Said
Acidic ion liquid is for being positively charged ion with imidazolyl or pyridyl or quaternary ammonium salt base, with [HSO
4]
-, [H
2PO
4]
-, [EtOSO
3]
-, [(EtO)
2PO
2]
-, [CF
3CO
2]
-, [BF
6]
-, [PF
6]
-, [OTf]
-, [TsO]
-, [ClO
4]
-, Ac
-, NO
3 -Or Cl
-Deng the ionic liquid of forming for negatively charged ion.
Said imidazolyl positively charged ion can be: [(CH
2)
3SO
3HMIM]
+, [(CH
2)
4SO
3HMIM]
+, [C
7MIM]
+, [BMIM]
+, [BMMIM]
+, [RMIM]
+, [MMIM]
+, [AMIM]
+, [EMIM]
+, [EMMIM]
+, [HMIM]
+, [PMIM]
+, [PMMIM]
+, [OMIM]
+, [EEIM]
+, [BEIM]
+, [AEIM]
+, [VMIM]
+, [C
5MIM]
+, [EOEIM]
+, [MOMIM]
+, [BzMIM]
+, [HOOCMIM]
+, [AOEMIM]
+, [AOMMIM]
+, or [1,2-Me-3-PIM]
+Deng;
Said pyridyl positively charged ion can be: [(CH
2)
4SO
3HPy]
+, [(CH
2)
4SO
3HPy]
+, [BuPy]
+, [EtPy]
+, [HPy]
+Or [OPy]
+Deng;
Said quaternary ammonium salt base positively charged ion can be: [(CH
2)
4SO
3HEt
3N]
+, [(CH
2)
3SO
3HEt
3N]
+, [(n-C
3H
7) Me
3N]
+, [(n-C
6H
13) Et
3N]
+, [(n-C
8H
17) Et
3N]
+, [(n-C
8H
17) (C
4H
9)
3N]
+, [(MeOCH
2) Me
3N]
+, or [(n-C
4H
9) Me
3N]
+Deng.
Said
acidic ion liquid can be represented with following structural formula:
R=CH in the formula (I)
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
7H
15, C
8H
17, C
10H
21, C
12H
25, C
14H
29, C
16H
33X=HSO
4, H
2PO
4
R=C in the formula (II)
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
7H
15, C
8H
17, C
10H
21X=HSO
4, H
2PO
4
N=2 in the formula (III); X=HSO
4, H
2PO
4
N=2 in the formula (IV); X=HSO
4, H
2PO
4
R=CH in the formula V
3, C
2H
5X=HSO
4, H
2PO
4
R=CH in the formula (VI)
3, C
2H
5X=HSO
4, H
2PO
4
R=CH in the formula (VII)
3, C
2H
5X=HSO
4, H
2PO
4
N=2 in the formula (VIII); X=HSO
4, H
2PO
4
N=3 in the formula (IX), 4; X=HSO
4, H
2PO
4, CF
3COO, OTf;
N=3 in the formula (X); X=HSO
4, H
2PO
4
In the formula (XI), R=CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
7H
15, C
8H
17, C
10H
21, C
12H
25, C
14H
29, C
16H
33
X＝BF
4，PF
6，EtOSO
3，(EtO)
2PO
2、CF
3CO
2，OTf、TsO，ClO
4，Ac，NO
3，Cl；
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
R=C in the formula (XII)
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
7H
15, C
8H
17, C
10H
21
X＝BF
4，PF
6，C
12SO
3，OTf，TsO，ClO
4，NO
3，Cl；
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
N=2 in the formula (XIII);
X＝BF
4，PF
6，OTf，TsO，ClO
4，NO
3，Cl；
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
N=2 in the formula (XIV);
X＝BF
4，PF
6，OTf，TsO，ClO
4，NO
3，Cl；
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
R=CH in the formula (X V)
3, C
2H
5
X＝BF
4，PF
6，OTf，TsO，NO
3；
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
R=CH in the formula (XVI)
3, C
2H
5
X＝BF
4，PF
6，OTf，TsO，ClO
4，NO
3，Cl；
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
R=CH in the formula (XVII)
3, C
2H
5X=BF
4, PF
6, NO
3, Cl;
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
R=C in the formula (XVIII)
2H
5, C
4H
9, C
6H
13, C
8H
17X=HSO
4, H
2PO
4
R=C in the formula (XIX)
3H
7, C
4H
9N=3,4; X=HSO
4, H
2PO
4
R=C in the formula (XX)
2H
5, C
4H
9, C
6H
13, C
8H
17
X＝BF
4，PF
6，ClO
4，OTf，TsO，NO
3；
X
1＝H
2SO
4，H
3PO
4，HF，HAc，HNO
3，HCl，TsOH；
R=CH in the formula (XXI)
3, C
2H
5, C
3H
7, C
4H
9
R
1＝CH
3，C
2H
5，C
3H
7，C
4H
9，C
6H
13，C
7H
7，C
8H
17，C
12H
25，C
16H
33，C
18H
35，
X＝HSO
4，H
2PO
4；
R=CH in the formula (XXII)
3, C
2H
5, C
3H
7, C
4H
9
n＝3，4；X＝HSO
4，H
2PO
4；
R=CH in the formula (XXIII)
3, C
2H
5, C
3H
7, C
4H
9
R
1＝H，CH
3，C
2H
5；n＝1，2；X＝HSO
4，H
2PO
4；
Said
acidic ionic liquid preparation:
In reactor drum, add glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate, stir, heating, reaction 8～24h; Reaction is cooled to room temperature (15 ℃～25 ℃) with reaction mixture after finishing, and filters; Washing separates, and is dried to constant weight and (as places vacuum drying oven; 90 ℃, 0.01Mpa), obtain the exsiccant midbody; With a certain amount of midbody dissolving, slowly drip a certain amount of protonic acid (like sulfuric acid or phosphoric acid etc.), heating; Stir, reaction 5～7h is after reaction finishes; Reaction solution is evaporated away redundant moisture (as using Rotary Evaporators), and the product that obtains is dried to constant weight and (as places vacuum drying oven, 90 ℃; 0.01Mpa), promptly get.
The mol ratio of described glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate is preferably 1: 0.80～and 1: 1.45, more preferably mol ratio is 1: 1.25.
The temperature of the reaction of described glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate is preferably 15～50 ℃, and more preferably temperature is 40 ℃.
The time of the reaction of described glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate is preferably 8～24h, and more preferably the time is 12h.
Said glyoxaline compound is imidazoles, N-Methylimidazole, DMIZ 1,2 dimethylimidazole, N-ethyl imidazol(e), N-propyl imidazole, N-NSC 158165, N-hexyl imidazoles, N-decyl imidazoles, N-octyl group imidazoles, N-dodecyl imidazoles, N-tetradecyl imidazoles or vinyl imidazole etc.;
Said pyridine compounds and their is pyridine or N-picoline etc.;
Said tertiary amine compounds is Trimethylamine 99, triethylamine, Tributylamine or tripropyl amine etc.;
Said alkylate is 1; 4-butane sultones, 1,3-N-morpholinopropanesulfonic acid lactone, chloropropane, iodopropane, n-propyl bromide, chlorobutane, NBB, bromooctane, chloroethyl ethyl ether, chloroethyl methyl ether, chloromethyl ethyl ether, chloromethyl methyl ether, methyl chloride, monobromethane, bromohexane, chlorohexane, monochloroethane, monobromethane, chloropentane, bromo pentane, heptyl bromide, chloroheptane, methyl iodide, iodoethane, butyl iodide, iodopentane, iodine heptane, iodo-octane, chlorinated dodecane, bromotetradecane, bromohexadecane, bromo-octadecane, vinylchlorid, benzyl chloride, glycol chlorohydrin, Mono Chloro Acetic Acid, bromoacetic acid, bromoethanol, chlorallylene, allyl bromide 98 or chloromethyl cyanide etc.
The solvent that washs in described preparation
the acidic ion liquid process is preferably organic solvent washings such as benzene, toluene, ETHYLE ACETATE or ether, and more preferably cleaning solvent is a toluene;
The preferred water of described midbody, hexanaphthene or methyl alcohol dissolve, and carry out next step reaction again;
The amount of said dropping protonic acid (like sulfuric acid, phosphoric acid etc.) and the mol ratio of midbody be preferably 1: 1.00～and 1: 1.10, more preferably mol ratio is 1: 1.01;
Described protonic acid (like sulfuric acid, phosphoric acid etc.) is preferably 60 ℃～85 ℃ with the temperature of midbody reaction, and more preferably temperature is 80 ℃;
Described protonic acid (like sulfuric acid, phosphoric acid etc.) is preferred 5.0～7.0h with the time of midbody reaction, and more preferably the reaction times is 6.0h;
The compound method of wallantoin of the present invention is the synthetic optimised process that carried out further investigation and on the basis of repeatedly experiment obtain of applicant to wallantoin; As catalyzer, have the advantage that traditional catalyst does not have with ionic liquid, it has the high-density reaction active site of liquid acid and the non-volatility of solid acid simultaneously; Acidity can surpass solid super-strong acid and can regulate catalyzer and product separate easily, Heat stability is good as required; Kind is many; Have adjustability of structure, and its physicochemical property depending on the zwitterion kind of application to a great extent, is truly programmable green solvent and catalyzer; And ionic liquid has the potentiality that replace the traditional industry catalyzer, and its meliority more and more obtains people's attention.This method is compared with traditional compound method, and yield is improved, and this ionic liquid can be reused simultaneously, not only in environment protection, has accomplished zero emission, and on cost, has also saved starting material greatly.The present invention uses ionic liquid to be catalyzer first in the technology of synthetic allantoin, and technical process is simple, and raw material is large industrial chemicals; Yield is high, is easy to industrialization promotion, the wallantoin stable yield; Yield can reach more than 68%, and catalyst ion liquid can be reused more than 5 times; And this technology is pollution-free, and energy-saving and environment friendly has good ecologic effect, good social and economic benefit.
The present invention is synthetic to
acid ion; Be on forefathers' basis, to have carried out further groping; Further optimization has been carried out in the ion liquid proportioning raw materials of synthetic, process control, and obtained
acid ion catalyzer of stability and high efficiency.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description.But do not limit the present invention with this.
Comparative Examples:
In reactor drum, add aqueous glyoxylic acid and urea, wherein, the mass concentration of aqueous glyoxylic acid is 45%, and quality is 822g (5.0mol); Stir, add the urea of 1260g (21.0mol) again, the mol ratio of oxoethanoic acid and urea is 1: 4.2, and reaction solution is heated to 68 ℃; Behind the reaction 6.5h, stop heating, be cooled to 15 ℃, filter and obtain white solid; With 1L deionized water wash solid, washed twice, the white solid that obtains is wallantoin; Taking-up places 100 ℃ of oven for drying, the 471g that weighs, and calculating productive rate is 50.62%.
Embodiment 1
(1) ion liquid preparation:
With 850g 1,4-butane sultones drips the 410gN-Methylimidazole under 25 ℃ gradually in the there-necked flask of 2L; Dropwise in the 30min, reaction solution is heated to 40 ℃, stir 12h; Filtration obtains white solid, is placed in the 1.6L toluene and stirs 15min, suction filtration; The bullion that obtains is placed vacuum drying oven (90 ℃ dry to constant weight under the 0.01Mpa); Obtain midbody 919g.Get above-mentioned resulting white powder solid 584g, add in the there-necked flask of 2L, add the 1.1L dissolve with methanol; Slowly drip sulfuric acid (massfraction 98%) 265g; After dropwising temperature is remained on 80 ℃, reaction 6h is after reaction finishes; Reaction solution is evaporated away redundant moisture with Rotary Evaporators, the [(CH that obtains
2)
4SO
3HMIM] [HSO
4], be placed on (90 ℃, 0.01Mpa is dried to constant weight) in the vacuum drying oven, obtain 648g.Be this and react needed ionic-liquid catalyst A.
(2) wallantoin is synthetic:
In reactor drum, add aqueous glyoxylic acid, urea and a certain proportion of catalyst A, wherein, the mass concentration of aqueous glyoxylic acid is 45%, and quality is 822g (5.0mol); Stir, add the urea of 1260g (21.0mol) again, the mol ratio of oxoethanoic acid and urea is 1: 4.2, stops heating when reaction solution is heated to 50 ℃; System's insulation, adding the catalyst A quality is 610g (2.0mol) (mol ratio of oxoethanoic acid and catalyzer is 1: 0.4), makes system be warmed up to 68 ℃, continues to stir; Behind the reaction 6.5h, stop heating, be cooled to 15 ℃, filter and obtain white solid; With 1L deionized water wash solid, wash three times (each 1L), merge washing lotion and filtrating, concentrated dewatering; Place the vacuum drying oven inner drying subsequent use, the white solid that obtains is wallantoin, takes out to place 100 ℃ of oven for drying; The 600g that weighs, calculating productive rate is 75.95%, is labeled as first batch.
Embodiment 2
After the ionic liquid drying with embodiment 1 reaction collection, add methyl alcohol 2.0L, reflux 2h, after the end that refluxes, cooling, filtration; Obtain filtrating concentrating, separation of methanol (can get time use ready) obtains reusing 1 time ionic liquid A1, adds aqueous glyoxylic acid and urea, and the mol ratio of oxoethanoic acid and urea is 1: 4.2; With reaction solution heat temperature raising to 68 ℃, reaction 6.5h stops heating, is cooled to 15 ℃; Filtration obtains white solid, with 1L deionized water wash solid, washs three times (each 1L), merges washing lotion and filtrating; Concentrate and anhydrate, obtain reusable ionic liquid, place the vacuum drying oven inner drying subsequent use, the white solid that reaction obtains is the product wallantoin; Taking-up places 100 ℃ of oven for drying, weighs, and calculating productive rate is 75.06%, is labeled as second batch.Can reuse three times according to this ionic liquid of this method, yield is respectively again: 74.68% (being labeled as the 3rd batch), 73.92% (being labeled as the 4th batch); 68.73% (being labeled as the 5th batch).
The wallantoin product that embodiment 1,2 is obtained is according to the methods analyst of USP the 29th edition (USP29), its result such as following table:
Embodiment 3
(1) ion liquid preparation:
With 850g 1,4-butane sultones drips the 395g pyridine under 25 ℃ gradually in the there-necked flask of 2L; Dropwise in the 30min, reaction solution is heated to 40 ℃, stir 12h; Filtration obtains white solid, is placed in the 1.6L toluene and stirs 15min, suction filtration; Place vacuum drying oven (90 ℃ dry to constant weight under the 0.01Mpa) to obtain midbody 896g the bullion that obtains; Get above-mentioned resulting white powder solid 578g, add in the there-necked flask of 2L, add the 1.1L deionized water dissolving; Slowly drip sulfuric acid (massfraction 98%) 265g; After dropwising temperature is remained on 80 ℃, reaction 6h is after reaction finishes; Reaction solution is evaporated away redundant moisture with Rotary Evaporators, the [(CH that obtains
2)
4SO
3HPy] [HSO
4], be placed on (90 ℃, 0.01Mpa is dried to constant weight) in the vacuum drying oven, obtain 650g, be the ionic-liquid catalyst B of this reaction needed.
(2) wallantoin is synthetic:
Technological process is identical with embodiment 1, and used catalyzer is B, and the yield of wallantoin is 73.29%, and the analytical results that obtains product is following:
Embodiment 4
(1) ion liquid preparation:
With 850g 1,4-butane sultones in the there-necked flask of 2L, Dropwise 5 06g triethylamine gradually under 25 ℃; Dropwise in the 30min, reaction solution is heated to 40 ℃, stir 12h; Filtration obtains white solid, is placed in the 1.6L toluene and stirs 15min, suction filtration; Place vacuum drying oven (90 ℃ dry to constant weight under the 0.01Mpa) to obtain midbody 1074g the bullion that obtains; Get above-mentioned resulting white powder solid 637g, add in the there-necked flask of 2L, add the dissolving of 1.1L hexanaphthene; Slowly drip sulfuric acid (massfraction 98%) 265g; After dropwising temperature is remained on 80 ℃, reaction 6h is after reaction finishes; Reaction solution is evaporated away redundant moisture with Rotary Evaporators, the [(CH that obtains
2)
4SO
3HEt
3N] [HSO
4], be placed on (90 ℃, 0.01Mpa is dried to constant weight) in the vacuum drying oven, obtain 710g, be the ionic-liquid catalyst C of this reaction needed.
(2) wallantoin is synthetic:
Technological process is identical with embodiment 1, and used catalyzer is C, and the yield of wallantoin is 72.03%, and the analytical results that obtains product is following:
Embodiment 5
(1) ion liquid preparation:
Method is identical with embodiment 1,3,4, and with 1,4-butane sultones is in the there-necked flask of 2L; Drip N-Methylimidazole, pyridine, triethylamine under 25 ℃ respectively gradually, dropwise in the 30min, reaction solution is heated to 40 ℃; Stir 12h, filter and obtain white solid, be placed on and stir 15min in the toluene; Suction filtration places vacuum drying oven (90 ℃ dry to constant weight under the 0.01Mpa) to obtain midbody the bullion that obtains; The above-mentioned white powder solid that obtains of a part is taken out in the there-necked flask that adds 2L; With methyl alcohol, water, hexanaphthene dissolving, slowly drip phosphoric acid (massfraction 85%) 306g respectively, after dropwising temperature is remained on 80 ℃; Reaction 6h; Reaction is evaporated away unnecessary solvent with reaction solution with Rotary Evaporators after finishing, and promptly obtains [(CH
2)
4SO
3HMIM] [H
2PO
4], [(CH
2)
4SO
3HPy] [H
2PO
4], [(CH
2)
4SO
3HEt
3N] [H
2PO
4], be placed on (90 ℃, 0.01Mpa is dried to constant weight) in the vacuum drying oven, be ionic-liquid catalyst D, E, the F of this reaction needed.
(2) wallantoin is synthetic:
Technological process is identical with embodiment 1, and used catalyzer is D, E, F, and the quality and the yield that obtain wallantoin are as shown in the table, and catalyzer also can be reused, and yield is basicly stable, and quality product is qualified.
| Catalyzer | Catalyzer D | Catalyzer E | Catalyzer F |
| Quality product (g) | ?573 | ?557 | ?555 |
| Yield (%) | ?72.53 | ?70.51 | ?70.25 |
Embodiment 6
(1) ion liquid synthetic
Method such as embodiment 1 are identical, the catalyst A that obtains
(2) wallantoin is synthetic
In reactor drum, add aqueous glyoxylic acid, urea and a certain proportion of catalyzer, wherein, the mass concentration of aqueous glyoxylic acid is 20%, and quality is 1850g (5.0mol); The urea that adds 1140g (19mol) again, the mol ratio of oxoethanoic acid and urea are 1: 3.8, stop heating when reaction solution is heated to 50 ℃, system's insulation; Adding the catalyst A quality is 763g (2.5mol) (mol ratio of oxoethanoic acid and catalyzer is 1: 0.5), makes system be warmed up to 55 ℃, continues to stir, behind the reaction 24h; Stop heating, be cooled to 15 ℃, filter and obtain white solid; With 1L deionized water wash solid, wash three times (each 1L), the white solid that obtains is wallantoin; Taking-up places 105 ℃ of oven for drying, the 561g that weighs, and calculating productive rate is 71.01%.
Embodiment 7
(1) ion liquid synthetic
Method such as embodiment 6 are identical, the catalyzer D ([(CH that obtains
2)
4SO
3HMIM] [H
2PO
4]).
(2) wallantoin is synthetic
In reactor drum, add aqueous glyoxylic acid, urea and a certain proportion of catalyzer, wherein, the mass concentration of aqueous glyoxylic acid is 40%, and quality is 925g (5.0mol); Stir, add the urea of 1350g (22.5mol) again, the mol ratio of oxoethanoic acid and urea is 1: 4.5, stops heating when reaction solution is heated to 60 ℃; System's insulation, adding catalyzer D quality is 783g (2.5mol) (mol ratio of oxoethanoic acid and catalyzer is 1: 0.5), makes system be warmed up to 80 ℃, continues to stir; Behind the reaction 24h, stop heating, be cooled to 15 ℃, filter and obtain white solid; With 1L deionized water wash solid, wash three times (each 1L), the white solid that obtains is wallantoin; Taking-up places 105 ℃ of oven for drying, the 557g that weighs, and calculating productive rate is 70.51%.
Claims (15)
1. the compound method of a wallantoin; It is characterized in that; With
acidic ion liquid is catalyzer, is the raw material synthetic allantoin with oxoethanoic acid and urea.
2. according to the compound method of the said wallantoin of claim 1, it is characterized in that the compound method of said wallantoin comprises, in reactor drum, adds aqueous glyoxylic acid, urea and catalyzer, stir, heating; Behind reaction 4.0～24.0h, reaction mixture is cooled to room temperature, filters, wash, oven dry obtains finished product; To filtrate and washing lotion merges collection and treatment and obtains catalyzer, repeat catalysis next time.
3. according to the compound method of the said wallantoin of claim 2, it is characterized in that the mass concentration of said aqueous glyoxylic acid is 20%～80%, the mass concentration of preferred aqueous glyoxylic acid is 20%～60%; More preferably the mass concentration of aqueous glyoxylic acid is 40%～50%.
4. according to the compound method of the said wallantoin of claim 2, it is characterized in that the mol ratio of said oxoethanoic acid and urea is 1: 2.0～1: 4.5, the mol ratio of preferred oxoethanoic acid and urea is 1: 3.5～1: 4.5; More preferably the mol ratio of oxoethanoic acid and urea is 1: 3.8～1: 4.3; The mol ratio of better preferred oxoethanoic acid and urea is 1: 4.0～1: 4.3.
5. according to the compound method of the said wallantoin of claim 2, it is characterized in that the mol ratio of said oxoethanoic acid and catalyzer is 1: 0.2～1: 0.5, the mol ratio of preferred oxoethanoic acid and catalyzer is 1: 0.3～0.4.
6. according to the compound method of the said wallantoin of claim 2, it is characterized in that said Heating temperature is 40 ℃～80 ℃, preferred Heating temperature is 60 ℃～70 ℃; More preferably Heating temperature is 66 ℃～68 ℃.
7. according to the compound method of the said wallantoin of claim 2, it is characterized in that the described reaction times is 4.0～24.0h, the preferred reaction time is 5.0～12.0h, and more preferably the reaction times is 5.5～7.0h, and the best preferred reaction time is 6.5h;
8. according to the compound method of the arbitrary said wallantoin of claim 1～7, it is characterized in that, said
Acidic ion liquid is for being positively charged ion with imidazolyl or pyridyl or quaternary ammonium salt base, with [HSO
4]
-, [H
2PO
4]
-, [EtOSO
3]
-, [(EtO)
2PO
2]
-, [CF
3CO
2]
-, [BF
6]
-, [PF
6]
-, [OTf]
-, [TsO]
-, [ClO
4]
-, Ac
-, NO
3 -, or Cl
-Ionic liquid for the negatively charged ion composition.
9. the compound method of said wallantoin according to Claim 8 is characterized in that,
Said imidazolyl positively charged ion is: [(CH
2)
3SO
3HMIM]
+, [(CH
2)
4SO
3HMIM]
+, [C
7MIM]
+, [BMIM]
+, [BMMIM]
+, [RMIM]
+, [MMIM]
+, [AMIM]
+, [EMIM]
+, [EMMIM]
+, [HMIM]
+, [PMIM]
+, [PMMIM]
+, [OMIM]
+, [EEIM]
+, [BEIM]
+, [AEIM]
+, [VMIM]
+, [C
5MIM]
+, [EOEIM]
+, [MOMIM]
+, [BzMIM]
+, [HOOCMIM]
+, [AOEMIM]
+, [AOMMIM]
+, or [1,2-Me-3-PIM]
+
Said pyridyl positively charged ion is: [(CH
2)
4SO
3HPy]
+, [(CH
2)
4SO
3HPy]
+, [BuPy]
+, [EtPy]
+, [HPy]
+Or [OPy]
+
Said quaternary ammonium salt base positively charged ion is: [(CH
2)
4SO
3HEt
3N]
+, [(CH
2)
3SO
3HEt
3N]
+, [(n-C
3H
7) Me
3N]
+, [(n-C
6H
13) Et
3N]
+, [(n-C
8H
17) Et
3N]
+, [(n-C
8H
17) (C
4H
9)
3N]
+, [(MeOCH
2) Me
3N]
+, or [(n-C
4H
9) Me
3N]
+
10. according to the compound method of the said wallantoin of claim 1～8, it is characterized in that said
acidic ionic liquid preparation: in reactor drum, add glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate; Stir; Heating, reaction 8～24h is after reaction finishes; Reaction mixture is cooled to room temperature; Filter, washing separates; Be dried to constant weight, obtain the exsiccant midbody; With the midbody dissolving, slowly drip protonic acid, heating is stirred, reaction 5～7h, reaction is evaporated away redundant moisture with reaction solution after finishing, and the product that obtains is dried to constant weight, promptly gets.
11. compound method according to the said wallantoin of claim 10; It is characterized in that; The mol ratio of described glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate is preferably 1: 0.80～and 1: 1.45, more preferably mol ratio is 1: 1.25.
12. the compound method according to the said wallantoin of claim 10 is characterized in that, the temperature of the reaction of described glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate is preferred 15～50 ℃, and more preferably temperature is 40 ℃; The time of the reaction of described glyoxaline compound or pyridine compounds and their or tertiary amine compounds and alkylate is preferred 8～24h, and more preferably the time is 12h.
13. the compound method according to the said wallantoin of claim 10～12 is characterized in that,
Said glyoxaline compound is imidazoles, N-Methylimidazole, DMIZ 1,2 dimethylimidazole, N-ethyl imidazol(e), N-propyl imidazole, N-NSC 158165, N-hexyl imidazoles, N-decyl imidazoles, N-octyl group imidazoles, N-dodecyl imidazoles, N-tetradecyl imidazoles or vinyl imidazole;
Said pyridine compounds and their is pyridine or N-picoline;
Said tertiary amine compounds is Trimethylamine 99, triethylamine, Tributylamine or tripropyl amine.
14. the compound method according to the said wallantoin of claim 10～13 is characterized in that,
The solvent that washs in described preparation
the acidic ion liquid process is benzene, toluene, ETHYLE ACETATE or ether.
15. the compound method according to the said wallantoin of claim 10～13 is characterized in that,
The preferred water of said midbody, hexanaphthene or methyl alcohol dissolve;
The amount of described dropping protonic acid and the mol ratio of midbody are 1: 1.00～1: 1.10, and preferred molar ratio is 1: 1.01;
The temperature of described protonic acid and midbody reaction is 60 ℃～85 ℃;
The time of described protonic acid and midbody reaction is 5.0～7.0h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103724272A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN103724273A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN103724274A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Compound catalyst allantoin synthesis method |
| CN107721932A (en) * | 2017-11-09 | 2018-02-23 | 上海纳米技术及应用国家工程研究中心有限公司 | The method of purifying ampholytic ionic liquid presoma |
| CN109401814A (en) * | 2018-12-26 | 2019-03-01 | 诺泰生物科技(合肥)有限公司 | P t butylbenzoic acid alkanolamide class corrosion inhibitor and its synthetic method and the application in extraordinary oil |
| CN111808025A (en) * | 2020-08-04 | 2020-10-23 | 李金国 | Preparation method of allantoin for cosmetics |
| CN111848522A (en) * | 2020-08-04 | 2020-10-30 | 李金国 | A method for producing allantoin for cosmetic |
| CN111848523A (en) * | 2020-08-04 | 2020-10-30 | 李金国 | A method for preparing allantoin for cosmetic |
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| CN103724272A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN103724273A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Allantoin synthesis method |
| CN103724274A (en) * | 2013-12-10 | 2014-04-16 | 芜湖华海生物工程有限公司 | Compound catalyst allantoin synthesis method |
| CN107721932A (en) * | 2017-11-09 | 2018-02-23 | 上海纳米技术及应用国家工程研究中心有限公司 | The method of purifying ampholytic ionic liquid presoma |
| CN109401814A (en) * | 2018-12-26 | 2019-03-01 | 诺泰生物科技(合肥)有限公司 | P t butylbenzoic acid alkanolamide class corrosion inhibitor and its synthetic method and the application in extraordinary oil |
| CN111808025A (en) * | 2020-08-04 | 2020-10-23 | 李金国 | Preparation method of allantoin for cosmetics |
| CN111848522A (en) * | 2020-08-04 | 2020-10-30 | 李金国 | A method for producing allantoin for cosmetic |
| CN111848523A (en) * | 2020-08-04 | 2020-10-30 | 李金国 | A method for preparing allantoin for cosmetic |
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