CN108484398B - Preparation method of 4-halobutyl acetate - Google Patents

Preparation method of 4-halobutyl acetate Download PDF

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CN108484398B
CN108484398B CN201810294883.XA CN201810294883A CN108484398B CN 108484398 B CN108484398 B CN 108484398B CN 201810294883 A CN201810294883 A CN 201810294883A CN 108484398 B CN108484398 B CN 108484398B
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陈正军
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    • C07C67/00—Preparation of carboxylic acid esters
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Abstract

A preparation method of 4-halobutyl acetate relates to a preparation method of acetate. The invention aims to solve the technical problems of long reaction time, high reaction temperature, high cost, use of toxic reagents, complex operation and low yield in the existing method for preparing 4-halobutyl acetate. The invention comprises the following steps: mixing urea, tetrahydrofuran and acetyl halide, stirring, naturally cooling to room temperature, adding distilled water, regulating to neutrality, vacuum filtering, extracting, drying, filtering and distilling. The 4-halobutyl acetate prepared by the invention structurally contains ester groups and chain-end halogens, and is a multifunctional compound with multiple purposes. The 4-halobutyl acetate prepared by the invention is prepared from corresponding acyl halide and cyclic ether under the catalysis of urea, and is a brand new preparation method. The solid by-product of the preparation process of the present invention is acylurea. The preparation method has the advantages of simple operation, low cost, safety, high efficiency, environmental friendliness and the like.

Description

Preparation method of 4-halobutyl acetate
Technical Field
The invention relates to a preparation method of acetate.
Background
4-halobutyl acetate is an ester containing a terminal haloalkyl group, structurally contains bifunctional groups of halogen and ester groups, and is an important organic compound and intermediate. The market price is very good (Bailingwei 2017 selling price: 4-chlorobutyl acetate is 770 yuan per 25 g of 350-. Can be used for synthesizing chemicals such as medicines [ J.Med.chem.2005,48(11): 3919-3929 ] [ US Patent 6627630,20030730 ] [ Tetrahedron letters.1986,27(7): 877-880 ], pesticides [ tetrahedron.1977,33: 1845-1889 ], perfumes [ US Patent 5786321,1998,7,28 ], dyes [ US Patent 6462204,20020808 ]. The following methods are available in the literature for the preparation of such compounds:
1. preparation from acyl halides and cyclic ethers
1939 [ J.Am.chem.Soc.1939,61(10): 2667-; if trace zinc chloride is added, refluxing for 30min to obtain chlorobutyl acetate with the yield of 71 percent; if refluxing is carried out for 12h without adding zinc chloride, 4-chlorobutyl acetate can be obtained in 45% yield. While subsequent literature reports that when no catalyst is used, acyl fluorides [ j.gen.chem. (u.s.s.r.) ] 1947,17: 416; chem.abstracts 1948, 42,858 and acid chloride chem.be.1942, 75B:537 no longer react with ether even when heated to 220 ℃.
[ J.Am.chem.Soc.1948,70: 1839-1842 ] reports that in the presence of anhydrous zinc chloride, not only acyl halide, phosphorus oxychloride, thionyl chloride, phosgene, silicon tetrachloride and the like can also react with tetrahydrofuran violently, but unfortunately, the corresponding products cannot be separated effectively, indicating the complexity of the reaction.
J.Prakt.chem.1932,134: 51-81 reports the reaction of acyl chlorides with ethers catalyzed by various Lewis acids, including zinc chloride and tin chloride (quantitative yield); titanium tetrachloride, zirconium tetrachloride, antimony pentachloride (about 83%); ferric chloride, aluminum chloride (about 50%); antimony trichloride (about 17%); boron trifluoride, copper chloride, stannous chloride (trace); silicon tetrachloride, phosphorus pentachloride, boron trichloride, arsenic trichloride, magnesium chloride (0), and the like. And [ J.chem.Soc.1951: 522-529 ] perchloric acid is superior to sulfuric acid when protonic acid is used for catalyzing the reaction of acyl chloride and ether. Furthermore [ chem.Ber.1942,75B:537 ] reported that pyridine has very weak catalytic activity. The zinc chloride-catalyzed reaction of acid chlorides with tetrahydrofuran is incorporated in organic synthesis [ org. syntheses.1949,29:30 ].
[ J.org.chem.1995,60: 745-747 ] catalyzing with 25 mol% of zinc powder, and reacting acyl chloride with cyclic ether or open-chain ether at room temperature for 1.5h in ether or petroleum ether under the protection of nitrogen to obtain the carboxylic ester with the terminal chlorocarbon group, wherein the yield is 70-90%.
[J.Org.Chem.2002,67:9488～9491.]Two equivalents of Smi under inert gas protection are reported2The equivalent amount of acyl chloride and cyclic ether are catalyzed to react for one hour at room temperature to obtain the carboxylic ester with the terminal iodine substituted alkyl, and the yield is 87%.
[J.Org.Chem.1983,48:751～753.]With Chuiss salt [ KPt (C)2H4)Cl3Or [ Rh (C)2H4)2Cl]2]Catalyzing acyl chloride to react with excessive tetrahydrofuran or dioxane and other cyclic ethers for 24 hours, and releasing heat to obtain the terminal chlorinated carboxylic ester with the yield of 19-83%. [ J.org.chem.1982,47: 1215-1220.]Tetrahydrofuran and acyl chloride in PhCH2Pd(PPh3)2Cl and (C)4H9)4Reaction in the presence of SnCl at 63 deg.C for 48 hours gave 85% -95% yield of 4-chlorocarboxylic acid ester, whereas tetrahydropyran gave a similar reaction yield of only 4%.
[ J.org.chem.,1973,38(1): 64-71 ] using hexacarbonyl compounds of Cr, Mo and W to catalyze the reaction of acyl chloride and cyclic ether to obtain the end-chlorinated carboxylic ester. Molybdenum triphenylphosphine complexes have similar catalytic activity. The reaction is carried out under reflux or under room temperature illumination, the reaction solvent is hexane or isooctane or no solvent, the reaction time is about 20 hours, and the reaction yield is about 54-88%. Wherein 2-methyltetrahydrofuran reacts with acetyl chloride to produce 4-chloropentyl acetate, the halogen being bonded to a carbon atom having a large degree of substitution. The optically pure 2-ethoxyoctane is reacted with acetyl chloride to obtain 2-chlorooctane as a product with reversed configuration.
In 1977 U.S. Pat. No. 4, 4005126,19770125 (U.S. Pat. No. 4,897) it was reported that acetates and other carboxylates of 4-halobutyl and 5-halopentyl were prepared by reacting a hydrohalogenic acid with an excess of an organic acid and an excess of tetrahydrofuran or tetrahydropyran at room temperature to 100 ℃ for 4 hours. The disadvantage of this process is mainly that the excess of reagent results in a large amount of waste.
U.S. Pat. No. 4, 9555008,20170131 (U.S. Pat. No. 2017) reported that 4-bromobutyl acetate was prepared by using acetonitrile as solvent and tetrahydrofuran stirred with acetyl chloride in the presence of a slight excess of potassium bromide at room temperature for 36 hours, giving a yield of 85% of 4-bromobutyl acetate.
2. Preparation from anhydrides and cyclic ethers
[ J.org.chem.1975,40(24): 3571-3574 ] reports that tetrahydrofuran and excess acetic anhydride were reacted at room temperature with stirring for 15h in acetonitrile using Grignard reagents prepared by the reaction of 1, 2-dibromoethane with magnesium metal to give 4-bromobutyl acetate in 97% yield. The method has the disadvantages of more reaction steps, harsh conditions, more reagent dosage, higher cost and toxic solvent.
3. From halogenated alcohols
The reaction of a halohydrin with a carboxylic acid derivative is the most direct reaction for preparing a halogen-containing carboxylic ester. [ US Patent 20040063758A1,20040401.]Reported as Br (CH)2)nOH (n ═ 3-9) and acetic anhydride are used as raw materials, and acetate with brominated hydrocarbon radicals at the tail ends is synthesized in the presence of pyridine. [ US Patent 8129552,20120306.]Terminal diols were reported to be monobrominated with 48% hydrobromic acid and then catalyzed with 10% 4- (N, N-dimethyl) aminopyridine with acetic anhydride in tetrahydrofuran at ambient temperatureThe reaction produced bromoacetate in 96% yield.
[Eur.J.Org.Chem.2003,23:4611～4617.]Report Zn (ClO)4)2The 9-bromo-1-heptanol and acetic anhydride are refluxed and reacted for 20min under the catalysis, and the acetic acid (9-bromo) heptyl ester with near quantitative yield is obtained. The main disadvantage of the process is that the corresponding halohydrins are relatively expensive.
4. Preparation from diols
[ J.org chem.1975,40(20): 2863-2870 ] reports that a mixture of hydrobromic acid, acetic acid and 1, 3-propylene glycol was stirred at room temperature for 30min to obtain 3-bromopropyl acetate with a yield of 67%. US Patent 5155256,19921013 and US Patent 5786321,19980728 report that acetic acid, glycol and hydrobromic acid mixtures can produce acetates with terminal brominated hydrocarbyl groups in yields of greater than 90% by reaction with water. [ Tetrahedron: Asymmetry,2005,16(15): 2607-2611 ] acetic acid (3-bromine) sec-butyl ester is prepared by a similar method, and the yield is 75-90%. [ application chemical industry, 2008,37(12): 1397-1400 ] 1, 4-butanediol, 48% hydrobromic acid and glacial acetic acid are used as raw materials, and 4-bromobutyl acetate is synthesized by reaction and water separation, wherein the yield is 91.2%.
5. Preparation from dihaloalkanes
[ J.Am.chem.Soc.1954,76: 2255-2256 ] report stirring 1, 3-dichloro-1-propoxybutane in dry benzene with sodium acetate for 14 hours at room temperature to give 3-chloro-1-propoxybutyl acetate in about 58% yield.
[ organic chemistry ] 1990,10(6):513 to 516 ] alpha, omega-dibromoalkane is dissolved in acetonitrile, and a mixed solution of glacial acetic acid and triethylamine is dropwise added under heating to synthesize 3-bromopropyl acetate, 4-bromobutyl acetate and 6-bromohexyl acetate with the yield of 34 to 42%.
Dissolving 1, 3-dibromopropane in ethanol, slowly dropwise adding an ethanol solution of potassium acetate at a reflux temperature, continuously refluxing and reacting for 2 hours after dropwise adding, and then stirring at room temperature for 12 hours to obtain 3-bromopropyl acetate with the yield of 44.3%.
6. Preparation by reaction of ethylene with aldehydes
And (Jan: 4069232,1978-01-17.) introducing ethylene gas into a mixed solution of formaldehyde, acetic acid and hydrobromic acid, and heating and stirring to obtain a mixture of 3-bromopropyl acetate and 3-bromo-1-propanol.
7. Preparation by thermal decomposition of metal-organic compounds
[ US Patent 4260814,19810407 ] reports that antimony dibromo alkyl dicarboxylate is thermally decomposed in carboxylic acid or acetonitrile at 100-200 ℃ to obtain bromo acetate with a yield of 24-79%. The raw materials of the method are not easy to obtain.
8. Preparation of terminal keto acid by reaction with bromine under catalysis of mercuric oxide
[Chemistry of Natural Compounds.2006,2(6):727～729.]Reported in N2Under protection, 10-acetyl decanoic acid, Br2And HgO in CCl4The 9-bromononyl acetate can be prepared by irradiating the mixture by a tungsten lamp and carrying out reflux reaction for 4 hours, and the yield is 78%.
[Russian Chemical Bulletin.1993,42(7):1246～1253.]First, CCl of 4-methyl-5-acetylvaleric acid, HgO was reported4Reacting the mixed solution at 50 ℃ for half an hour, and adding bromine CCl4The solution reacts for 100min at 65 ℃ to prepare the 2-methyl-4-bromobutyl acetate with the yield of 81 percent.
9. Preparation from ethers by acid decomposition
[ J.Soc.chem.Ind.Japan.1944,47:220 ] reports the reaction of tetrahydrofuran, hydrogen chloride and acetic acid in benzene to dichlorobutane and 4-chlorobutyl acetate.
[ British Patent 642,489; chem.abstracts.1952,46: 132: tetrahydrofuran, acetic acid, phosphorus trichloride and trace zinc chloride were refluxed at 120 ℃ for 2 hours to obtain chlorobutyl acetate with a yield of 80%.
The reported preparation method has the disadvantages of large dosage of reaction reagents, long reaction time, high reaction temperature, selection of expensive raw materials or use of toxic reagents, and the use of anhydrous Lewis acid catalysis, which not only has large dosage of catalysts, but also needs pretreatment of reagents and inert gas protection, and long reaction time, thus not only having complex operation and high cost, but also having poor yield.
Disclosure of Invention
The invention provides a preparation method of 4-halobutyl acetate, aiming at solving the technical problems of long reaction time, high reaction temperature, high cost, use of toxic reagents, complex operation and low yield in the existing preparation method of 4-halobutyl acetate.
The preparation method of the 4-halobutyl acetate is carried out according to the following steps:
adding urea and tetrahydrofuran into a reaction bottle provided with a thermometer, a stirring and reflux condenser pipe and a constant-pressure dropping funnel in sequence, adding acetyl halide through the constant-pressure dropping funnel under the stirring condition, stirring and reacting for 2-4 h under the condition of 20-70 ℃ after dropwise addition is finished, naturally cooling to room temperature, adding distilled water, adjusting the pH to 7-9 with an alkali solution, performing suction filtration to obtain a solid byproduct and a filtrate I respectively, extracting the filtrate I with ethyl acetate for three times, adding anhydrous sodium sulfate into an ethyl acetate extract for drying, filtering to obtain a filtrate II, and performing normal-pressure distillation or reduced-pressure distillation on the filtrate II to obtain the 4-halobutyl acetate.
When acetyl halide is acetyl chloride, colorless 4-chlorobutyl acetate is finally obtained, the normal pressure distillation condition is 196-198 ℃/760mmHg, and the reduced pressure distillation condition is 86-88 ℃/20 mmHg;
when acetyl halide of the invention is acetyl bromide, the final product is light yellow 4-bromobutyl acetate, the condition of atmospheric distillation is 214-215 ℃/760mmHg, and the condition of reduced pressure distillation is 74-75 ℃/12 mmHg.
The structural formula of the 4-halobutyl acetate prepared by the invention is as follows:
Figure BDA0001617682610000041
and X is Cl or Br.
The invention has the following beneficial effects:
the 4-halobutyl acetate prepared by the invention structurally contains ester groups and chain-end halogens, and is a multifunctional compound with multiple purposes.
The 4-halobutyl acetate prepared by the invention is prepared from corresponding acyl halide and cyclic ether (tetrahydrofuran) under the catalysis of urea, and is a brand new compound preparation method.
The solid by-product of the preparation method is acyl urea, and the yield can reach 61.18 percent at most. The preparation method has the advantages of simple operation, low cost, safety, high efficiency, environmental friendliness and the like, and the yield of the 4-halobutyl acetate can reach 75.19 percent to the maximum.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of 4-halobutyl acetate, which is specifically carried out according to the following steps:
adding urea and tetrahydrofuran into a reaction bottle provided with a thermometer, a stirring and reflux condenser pipe and a constant-pressure dropping funnel in sequence, adding acetyl halide through the constant-pressure dropping funnel under the stirring condition, stirring and reacting for 2-4 h under the condition of 20-70 ℃ after dropwise addition is finished, naturally cooling to room temperature, adding distilled water, adjusting the pH to 7-9 with an alkali solution, performing suction filtration to obtain a solid byproduct and a filtrate I respectively, extracting the filtrate I with ethyl acetate for three times, adding anhydrous sodium sulfate into an ethyl acetate extract for drying, filtering to obtain a filtrate II, and performing normal-pressure distillation or reduced-pressure distillation on the filtrate II to obtain the 4-halobutyl acetate.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the acetyl halide is acetyl chloride or acetyl bromide. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the alkali solution is NaOH aqueous solution or sodium carbonate aqueous solution. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the molar ratio of the urea to the tetrahydrofuran is 1 (1-20). The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the molar ratio of the urea to the acetyl halide is 1 (1-10). The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the volume ratio of the urea substance to the distilled water is 1mol (0.1L-3L). The rest is the same as one of the first to fourth embodiments.
The invention was verified with the following tests:
test one: the test is a preparation method of 4-halobutyl acetate, and the preparation method is specifically carried out according to the following steps:
sequentially adding urea and tetrahydrofuran into a three-neck flask provided with a thermometer, a stirring and reflux condenser pipe and a constant-pressure dropping funnel, adding acetyl halide through the constant-pressure dropping funnel under the stirring condition, stirring and reacting for 2 hours at 50 ℃ after dropwise addition is finished, naturally cooling to room temperature, adding distilled water, then adjusting the pH to 7 with an alkali solution, performing suction filtration to obtain a solid byproduct and a filtrate I, extracting the filtrate I with 20mL of ethyl acetate for three times, adding anhydrous sodium sulfate into an ethyl acetate extract for drying, filtering to obtain a filtrate II, performing reduced-pressure distillation on the filtrate II to obtain colorless 4-halobutyl acetate, wherein the yield is 65.92%;
the reduced pressure distillation condition is 86-88 ℃/20 mmHg;
the acetyl halide is acetyl chloride;
the alkali solution is NaOH aqueous solution;
the molar ratio of the urea to the tetrahydrofuran is 1: 6.48;
the molar ratio of the urea to the acetyl halide is 1: 3.3;
the volume ratio of the urea substance to the distilled water is 1mol: 0.87L.
The 4-halobutyl acetate prepared in the test is subjected to infrared absorption spectrum test, and the test data is as follows:
FT-IR(KBr,cm-1)：2960(νCH3)，2873(νCH3,νCH2)，1740(νC＝O)，1447(δasCH3)，1389(δsCH3) 1368 (bend λ δ sCH)3) 1239 (v C-O-C), 1045 (v C-O-C), 823, 751(ρ CH2, v C-Cl), 730 (in-plane rocking ρ CH2, vC-Cl)，651。
Mass spectrometry tests were performed on the 4-halobutyl acetate prepared in this experiment with the following test data:
GC-MS：150.5(M)，115(M-Cl)，107(M-CH3CO)，90(M-CH3COO)，73(CH3COOCH2 or OCH2CH2CH2CH2),63(CH2CH2Cl,),56(CH2CH2CH2CH2),43(CH3CO)。
the 4-halobutyl acetate prepared in the test is subjected to a nuclear magnetic resonance hydrogen spectrum test, and the test data is as follows:
1HNMR(CDCl3)：1.760～1.898(m，4H，-CH2-CH2-)，2.054(s，3H，CH3)，3.556～3.587(T，J＝0.0155×400＝6.2Hz,2H，CH2)，4.088～4.119(T，J＝0.0155×400＝6.2Hz,2H，CH2)。
from the above data, it can be determined that the 4-halobutyl acetate prepared in this experiment is 4-chlorobutyl acetate, having the formula:
Figure BDA0001617682610000061
the solid by-product of this test was dried to a white powder, which was subjected to infrared absorption spectroscopy, with the following test data:
FT-IR(KBr,cm-1):3379,3333,3209(νNH2,NH),2992,2985(νCH3)，1712,1693,1675(νC＝O,νC＝N),1485,1417(δNH2,δNH,νC-N),1366(δCH3),1250(νC-N,δNH)，1099,1034(νC-N,νC-OH)，942(γNH)，813(γNH2)，693(γNH)，569。
the melting point of the material is 216-218 ℃ by a capillary method.
The product was identified as acetylurea, with a 22.26% yield.
And (2) test II: the test is a preparation method of 4-halobutyl acetate, and the preparation method is specifically carried out according to the following steps:
sequentially adding urea and tetrahydrofuran into a three-neck flask provided with a thermometer, a stirring and reflux condenser pipe and a constant-pressure dropping funnel, adding acetyl halide through the constant-pressure dropping funnel under the stirring condition, stirring and reacting for 4 hours at the temperature of 60 ℃ after dropwise addition is finished, naturally cooling to room temperature, adding distilled water, then adjusting the pH to 8 with an alkali solution, performing suction filtration to obtain a solid byproduct and a filtrate I, extracting the filtrate I with 20mL of ethyl acetate for three times, adding anhydrous sodium sulfate into an ethyl acetate extract for drying, filtering to obtain a filtrate II, performing reduced pressure distillation on the filtrate II to obtain faint yellow 4-halobutyl acetate, wherein the yield is 75.19%;
the reduced pressure distillation condition is 74-75 ℃/12 mmHg;
the acetyl halide is acetyl bromide;
the alkali solution is sodium carbonate aqueous solution;
the molar ratio of the urea to the tetrahydrofuran is 1: 15;
the molar ratio of the urea to the acetyl halide is 1: 5;
the volume ratio of the urea substance to the distilled water is 1mol: 2L.
The 4-halobutyl acetate prepared in the test is subjected to infrared absorption spectrum test, and the test data is as follows:
FT-IR(KBr,cm-1)：2961(νCH3,νCH2)，1739(νC＝O)，1439(δasCH3)，1388(δsCH3)，1367(νλδυ)，1237(νC-O-C)，1042(νC-O-C)，948，873，749,646,606,561(ρCH2,νC-Br)，483。
mass spectrometry tests were performed on the 4-halobutyl acetate prepared in this experiment with the following test data:
GC-MS：195(M)，152(M-CH3CO),137(M-CH3CO2),115(M-Br)，108(CH2CH2Br),87(CH3COOCH2CH2)，73(CH3COOCH2or OCH2CH2CH2CH2),61(CH3COOH),56(CH2CH2CH2CH2),43(CH3CO)。
the 4-halobutyl acetate prepared in the test is subjected to a nuclear magnetic resonance hydrogen spectrum test, and the test data is as follows:
1HNMR(CDCl3)：1.764～1.833(m，J≈0.016×400＝6.4Hz,2H，-CH2-)，1.911～1.981(m，J≈0.016×400＝6.4Hz,2H，-CH2-)，2.054(s，3H，CH3)，3.423～3.456(T，J＝0.0165×400Hz,2H，CH2)，4.085～4.116(T，J＝0.0155×400Hz,2H，CH2)。
from the above data, it can be determined that the 4-halobutyl acetate prepared in this experiment is 4-bromobutyl acetate, of the formula:
Figure BDA0001617682610000081
the solid by-product of this test was dried to a white powder, which was subjected to infrared absorption spectroscopy, with the following test data:
FT-IR(KBr,cm-1):3379,3333,3209(νNH2,NH),2992,2985(νCH3)，1712,1693,1675(νC＝O,νC＝N),1485,1417(δNH2,δNH,νC-N),1366(δCH3),1250(νC-N,δNH)，1099,1034(νC-N,νC-OH)，942(γNH)，813(γNH2)，693(γNH)，569。
the melting point of the material is 216-218 ℃ by a capillary method.
Through identification, the product is determined to be acetylurea, and the yield of the acetylurea is 61.17%.

Claims (6)

1. A preparation method of 4-halobutyl acetate is characterized in that the preparation method of the 4-halobutyl acetate is carried out according to the following steps:
adding urea and tetrahydrofuran into a reaction bottle provided with a thermometer, a stirring and reflux condenser pipe and a constant-pressure dropping funnel in sequence, adding acetyl halide through the constant-pressure dropping funnel under the stirring condition, stirring and reacting for 2-4 h under the condition of 20-70 ℃ after dropwise addition is finished, naturally cooling to room temperature, adding distilled water, adjusting the pH to 7-9 with an alkali solution, performing suction filtration to obtain a solid byproduct and a filtrate I respectively, extracting the filtrate I with ethyl acetate for three times, adding anhydrous sodium sulfate into an ethyl acetate extract for drying, filtering to obtain a filtrate II, and performing atmospheric distillation or reduced-pressure distillation on the filtrate II to obtain the 4-halobutyl acetate.
2. The method according to claim 1, wherein the acetyl halide is acetyl chloride or acetyl bromide.
3. The method according to claim 1, wherein the alkali solution is NaOH aqueous solution or sodium carbonate aqueous solution.
4. The method for preparing 4-halobutyl acetate according to claim 1, wherein the molar ratio of urea to tetrahydrofuran is 1 (1-20).
5. The method for preparing 4-halobutyl acetate according to claim 1, wherein the molar ratio of urea to acetyl halide is 1 (1-10).
6. The process according to claim 1, wherein the volume ratio of urea to distilled water is 1mol (0.1L-3L).
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