WO1992009591A1 - Process for the preparation of 2-(2-bromo-2-nitroethenyl)furan - Google Patents

Process for the preparation of 2-(2-bromo-2-nitroethenyl)furan Download PDF

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Publication number
WO1992009591A1
WO1992009591A1 PCT/US1991/009018 US9109018W WO9209591A1 WO 1992009591 A1 WO1992009591 A1 WO 1992009591A1 US 9109018 W US9109018 W US 9109018W WO 9209591 A1 WO9209591 A1 WO 9209591A1
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Prior art keywords
butylamine
water
primary amine
group
schiff base
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PCT/US1991/009018
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French (fr)
Inventor
Fred R. Gerns
Larry D. Timberlake
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Great Lakes Chemical Corp
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Great Lakes Chemical Corp
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Priority claimed from US07/686,427 external-priority patent/US5138076A/en
Application filed by Great Lakes Chemical Corp filed Critical Great Lakes Chemical Corp
Priority to DE69122882T priority Critical patent/DE69122882T2/en
Priority to KR1019930701650A priority patent/KR930703280A/en
Priority to EP92902359A priority patent/EP0561994B1/en
Priority to JP4502684A priority patent/JPH06503575A/en
Priority to AU91181/91A priority patent/AU648628B2/en
Publication of WO1992009591A1 publication Critical patent/WO1992009591A1/en
Priority to FI932507A priority patent/FI101792B1/en
Priority to NO932013A priority patent/NO301761B1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms

Definitions

  • This invention relates to processes for the preparation of bromonitroethenyl furan, and particularly to a process which produces 2-(2-Bromo-2-nitroethenyl) furan (BNEF) in high purity and yield.
  • BNEF 2-(2-Bromo-2-nitroethenyl) furan
  • One process for producing BNEF comprises the reaction of furfural with bromonitromethane using a primary amine or primary amine salt and sodium carbonate as the catalytic agent at 10 mol% to produce an intermediate
  • 2-(2-Bromo-2-nitroethenyl) furan which comprises converting furfural to a Schiff base in an organic solvent, isolating the Schiff base by removing the organic solvent therefrom, dissolving the Schiff base in a polar, water-miscible solvent, reacting the Schiff base solution with
  • a further object is to provide a process which produces bromonitroethenylfuran in a high state of purity
  • This invention is concerned with a new and superior process for producing 2-(2-Bromo-2-nitroethenyl) furan.
  • the superiority of this process lies in the fact that the product is recovered in very high yield and assay, with a minimum of purification.
  • the prior art processes produced the compound in lower yields and required extensive and costly cleanup procedures.
  • the process of this invention broadly consists of the following steps.
  • the furfural is converted to its imine or Schiff base in an organic solvent, followed by removal of the organic solvent and concomittant removal of the water
  • the Schiff base is dissolved in a polar solvent and this solution is then reacted with bromonitromethane.
  • the product is isolated by diluting the reaction mixture with water to produce the BNEF as a precipitate, followed by filtering.
  • the amine is preferably an aliphatic amine such as n-butylamine, although aromatic amines are also suitable.
  • Suitable amines for reaction with the furfural are C 1 -C 8 primary a liphatic amines , primary
  • aryla lkylamines including benzylamine, chlorobenzylamine and methylbenzylamine, and aromatic primary amines including aniline, toluidine, p-chloroaniline and xylidene.
  • the preferred primary amine is an aliphatic one, which may more specifically include methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-amylamine, t-amylamine, 1-methylbutylamine and
  • 2-methylbutylamine of which the most preferred ones are n-butylamine, n-propylamine, ethylamine and n-amylamine. It will be appreciated that amines which are highly volatile can cause handling problems, and that amines having too high a boiling point are less desired in view of the subsequent distillation step. n-Butylamine performs well in this process.
  • the solvent and the water formed during conversion of the furfural is then removed from the Schiff base.
  • the organic solvent is preferably selected from the class of solvents which will form an azeotrope with water, and the water formed in the reaction is then removed along with the organic solvent by azeotropic distillation. When the theoretical amount of water has been collected, the organic solvent is stripped off. Appropriate organic solvents can be readily selected by those skilled in the art.
  • suitable organic solvents include cyclohexane, methylcyclohexane, methylene dichloride, ethylene dichloride, chloroform, benzene, toluene, o-xylenes, m-xylenes, p-xylenes, and aliphatic alcohols such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl alcohols.
  • aliphatic alcohols such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl alcohols.
  • solvents are cyclohexane, methylcyclohexane, toluene and methylene chloride.
  • the residual Schiff base is then dissolved in a polar, water-miscible solvent, preferably a water-miscible
  • Preferred water-miscible solvents include acetic acid and propionic acid.
  • Other appropriate solvents may be readily selected by one skilled in the art given the desired aspects described herein for such solvent.
  • the use of a water-miscible solvent permits a simple product isolation procedure involving quenching with water to precipitate the product in high yield and assay, followed by purification by a simple aqueous wash.
  • the use of a water-immiscible organic solvent would require stripping this solvent and recovery of a bottoms product contaminated with undesirable byproducts and therefore requiring extensive purification procedures.
  • BNEF forms as a precipitate from the reaction mixture during the hold period. Diluting the reaction mixture with water precipitates the remainder of the product. The product may then be isolated by
  • the Schiff base was formed in methanol, but in contrast to Example 3, the methanol was stripped off and replaced with acetic acid, followed by addition of bromonitromethane in accordance with the present invention. Good yields and high assay product were obtained.
  • the Schiff base 756.0 g (5.0 mols), was charged to a well-stirred, 5 liter, 5-neck round-bottom flask.
  • Acetic acid (1250 ml) was added in one-half hour at 15° C to 20° C. This was followed by the addition of 727.9 g (5.0 mols, 96.1% assay) of bromonitromethane at 15° C to 20° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Furan Compounds (AREA)

Abstract

Bromonitroethenylfuran (BNEF) is prepared from furfural in a two-step process. A primary amine is reacted with furfural in an organic solvent at the reflux temperature of the solvent to form the Schiff base. The organic solvent and the water formed in the foregoing reaction are removed from the Schiff base, which is then dissolved in a polar, water-miscible solvent. Bromonitromethane is added to the Schiff base solution and reacts with the Schiff base to form BNEF, which can be readily isolated by precipitation.

Description

PROCESS FOR THE PREPARATION OF
2-(2-BROMO-2-NITROETHENYL)FURAN
REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of United States Patent Application Serial No. 621,339, filed on
December 3, 1990 and entitled PROCESS FOR THE PREPARATION OF 2-(2-BROMO-2-NITROETHENYL)FURAN.
FIELD OF THE INVENTION
This invention relates to processes for the preparation of bromonitroethenyl furan, and particularly to a process which produces 2-(2-Bromo-2-nitroethenyl) furan (BNEF) in high purity and yield.
DESCRIPTION OF THE PRIOR ART
The use of 2-(2-Bromo-2-nitroethenyl)furan as an
antimicrobial with a broad spectrum of uses in water
treatment, pulp and paper manufacturing, metal working fluids and various non-oxidizing biocide applications has been described. One process for producing BNEF comprises the reaction of furfural with bromonitromethane using a primary amine or primary amine salt and sodium carbonate as the catalytic agent at 10 mol% to produce an intermediate
2-Bromo-1-(2-furyl)-2-nitroethanol, which is dehydrated in the presence of acid to the desired product. The preferred solvent is ethanol. In a typical procedure, the reaction mixture is stirred for 25 hours at 5° C, and the acid is then added to effect the dehydration. The reaction mixture is extracted with methylene chloride and the crude product recovered as an oil which is steam-distilled. The solid product is filtered from the steam-distillate and
recrystallized from ethanol, and the yield is reported to be in the range of 23%.
The major disadvantages of this process are the lengthy reaction times to form the intermediate which in a further step needs to be dehydrated, the need for extensive and costly purification procedures such as steam-distillation and recrystallization, the low yield, and the use of ethanol as the solvent. The use of ethanol as an industrial solvent is surrounded by many restrictions.
Another procedure for synthesis of bromonitroethenylfuran is described by Z.N. Nazarova and G.F. Potemkin in Khim.
Farm, Zh., v. 6 (10), pp. 629-632 (1972), "Synthesis of Some Furylnitroolefins with Potential Biological Activity". In accordance with this method, the appropriate 5-substituted furfural is condensed with bromonitromethane in the presence of KOH catalyst. Bromonitroethenylfuran, specifically, is synthesized as follows. To furfural and bromonitromethane in methanol is added a solution of KOH in water with cooling. The reaction mixture is kept in a cooling bath for 30
minutes, and water is then added and the mixture poured into dilute HCl. After 30 minutes, the precipitate (or oil) is separated, washed with water, purified by steam-distillation and recrystallized from ethanol. Reported yield is 70.5%. Attempts to duplicate these results in our laboratory were unsuccessful, resulting largely in unworkable tars with only traces of isolatable product.
A similar procedure for synthesizing methyl-nitroethenyl-and nitroethanylfurans is reported by Gruntfest, et al. in Zh. Org. Khim. vol. 7, pp. 1078-1082 (1971), cited in M.G. Gruntfest, et al., Zh. Pro. Khim., vol. 8, pp. 405-411 (1972) "Physicochemical Properties and Reactivities of
Furylnitroolefins". Equimolar quantities of furfural and nitroparaffin in methanol are treated with 2 moles of aqueous KOH. The mixture is acidified and the precipitate is
filtered off, washed and dried, and recrystallized from ethanol or steam-distilled. Yield and assay for the
bromonitroethenylfuran were not given.
In contrast to the prior art, the process of our
invention uses inexpensive industrial solvents, requires only a three-hour hold period, does not require steam-distillation or recrystallization, and provides a 94% yield of high-assay (greater than 98%) product.
SUMMARY OF THE INVENTION
Briefly describing one aspect of the present invention, there is provided a process for preparing
2-(2-Bromo-2-nitroethenyl) furan which comprises converting furfural to a Schiff base in an organic solvent, isolating the Schiff base by removing the organic solvent therefrom, dissolving the Schiff base in a polar, water-miscible solvent, reacting the Schiff base solution with
bromonitromethane, and isolating the
2-(2-Bromo-2-nitroethenyl)furan product from the reaction mixture.
It is an object of the present invention to provide an improved process for the production of
2-(2-Bromo-2-nitroethenyl) furan, a potent, broad-spectrum industrial, non-oxidizing microbiocide.
A further object is to provide a process which produces bromonitroethenylfuran in a high state of purity and
eliminates the need for steam distillation and
recrystallization, costly and cumbersome operations practiced in the prior art.
Further objects and advantages of the present invention will be apparent from the description which follows.
DESCRIPTION OF THE PREFERRED EMBODIMENT
For the purposes of promoting an understanding of the principles of the invention, reference will now be made to the preferred embodiment of the invention and specific language will be used to describe the same. It will
nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations,
modifications and further applications of the principles of the invention being contemplated as would normally occur to one skilled in the art to which the invention relates.
This invention is concerned with a new and superior process for producing 2-(2-Bromo-2-nitroethenyl) furan. The superiority of this process lies in the fact that the product is recovered in very high yield and assay, with a minimum of purification. In contrast, the prior art processes produced the compound in lower yields and required extensive and costly cleanup procedures.
The process of this invention broadly consists of the following steps. The furfural is converted to its imine or Schiff base in an organic solvent, followed by removal of the organic solvent and concomittant removal of the water
produced in the Schiff base formation. The Schiff base is dissolved in a polar solvent and this solution is then reacted with bromonitromethane. The product is isolated by diluting the reaction mixture with water to produce the BNEF as a precipitate, followed by filtering.
Conversion of furfural to its Schiff base is effected by reacting a primary amine with furfural in an organic
solvent. The amine is preferably an aliphatic amine such as n-butylamine, although aromatic amines are also suitable.
Further examples of suitable amines for reaction with the furfural are C1-C8 primary a liphatic amines , primary
aryla lkylamines including benzylamine, chlorobenzylamine and methylbenzylamine, and aromatic primary amines including aniline, toluidine, p-chloroaniline and xylidene. The preferred primary amine is an aliphatic one, which may more specifically include methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-amylamine, t-amylamine, 1-methylbutylamine and
2-methylbutylamine, of which the most preferred ones are n-butylamine, n-propylamine, ethylamine and n-amylamine. It will be appreciated that amines which are highly volatile can cause handling problems, and that amines having too high a boiling point are less desired in view of the subsequent distillation step. n-Butylamine performs well in this process.
The solvent and the water formed during conversion of the furfural is then removed from the Schiff base. The organic solvent is preferably selected from the class of solvents which will form an azeotrope with water, and the water formed in the reaction is then removed along with the organic solvent by azeotropic distillation. When the theoretical amount of water has been collected, the organic solvent is stripped off. Appropriate organic solvents can be readily selected by those skilled in the art. Examples of suitable organic solvents include cyclohexane, methylcyclohexane, methylene dichloride, ethylene dichloride, chloroform, benzene, toluene, o-xylenes, m-xylenes, p-xylenes, and aliphatic alcohols such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl alcohols. The preferred
solvents are cyclohexane, methylcyclohexane, toluene and methylene chloride.
The residual Schiff base is then dissolved in a polar, water-miscible solvent, preferably a water-miscible
carboxylic acid, for reaction with bromonitromethane.
Preferred water-miscible solvents include acetic acid and propionic acid. Other appropriate solvents may be readily selected by one skilled in the art given the desired aspects described herein for such solvent. The use of a water-miscible solvent permits a simple product isolation procedure involving quenching with water to precipitate the product in high yield and assay, followed by purification by a simple aqueous wash. On the other hand, the use of a water-immiscible organic solvent would require stripping this solvent and recovery of a bottoms product contaminated with undesirable byproducts and therefore requiring extensive purification procedures.
The Schiff base solution is then reacted with
bromonitromethane to form a reaction mixture including
2-(2-Bromo-2-nitroethenyl) furan. BNEF forms as a precipitate from the reaction mixture during the hold period. Diluting the reaction mixture with water precipitates the remainder of the product. The product may then be isolated by
conventional methods.
The following examples, tabulated below, demonstrate the improvements achieved by the present invention process and, in particular, the advantages of forming the Schiff base intermediate in providing high yield and assay of
bromonitroethenylfuran. It will be understood that these Examples are illustrative and not restrictive in nature.
Example 1
Using 10 mol% butylamine in methanol, analogous to the use of 10 mol% CH3NH2HCl/Na2CO3 in the prior art
process, bromonitromethane was reacted with furfural and butylamine without prior formation of the Schiff base. After several hours of stirring, under various conditions, the product was isolated and determined to have been produced in low yields. Example 2
This example as set forth in Table I demonstrates that using acetic acid as the solvent, rather than methanol, with catalytic amounts of amine, without prior formation of the
Schiff base, affords high-assay product but in very low yield.
Example 3
This example demonstrates that even when a stoichiometric amount of butylamine is used, unless the Schiff base is formed first and isolated by removing the solvent and the water formed, the product is recovered as a tar.
Stoichiometric quantities of furfural and butylamine were charged to methanol at 5-10° C in a nitrogen atmosphere.
After 20 minutes, bromonitromethane was added at 5° C. The reaction mixture was stirred at from 2° C to 28° C for 3 hours, then stored in the refrigerator. Upon quenching in water at 0-5° C, a black tar was recovered.
Example 4
In this example, the Schiff base was formed in methanol, but in contrast to Example 3, the methanol was stripped off and replaced with acetic acid, followed by addition of bromonitromethane in accordance with the present invention. Good yields and high assay product were obtained.
Stoichiometric quantities of furfural and butylamine were charged to methanol at 20-25° C under a nitrogen atmosphere. After 50 minutes of stirring at 23° C an additional 5 mol% of butylamine was added. However, this had no notable effect on the NMR profile. After holding overnight at ambient
temperature, the methanol and water were stripped off. The residual Schiff base was dissolved in acetic acid at 0° C, and bromonitromethane was then added at the same
temperature. After 2 hours of stirring at 26° C the reaction slurry was quenched in water, and the product was filtered, washed and dried. A yield of 89.4% of product was obtained, assaying 96.5%.
Example 5
This example further demonstrates the process of this invention. Furfural (1009.1 g; 10.5 mols) and 1000 ml of cyclohexane were charged to a 5 liter, 5-neck round-bottom flask. n-Butylamine, 768.0 g (10.5 mols), was added from a dropping funnel in 50 minutes, keeping the temperature below 60° C. The mixture was then heated at reflux for 4 hours, at which time the theoretical quantity of water had distilled over. The solution was then stripped at reduced pressure. The Schiff base intermediate was recovered as a bottoms product in 98.7 % yield (1567.5 g), assaying 99.4% by GC, and was used in the subsequent condensation without further purification.
The Schiff base, 756.0 g (5.0 mols), was charged to a well-stirred, 5 liter, 5-neck round-bottom flask. Acetic acid (1250 ml) was added in one-half hour at 15° C to 20° C. This was followed by the addition of 727.9 g (5.0 mols, 96.1% assay) of bromonitromethane at 15° C to 20° C. Upon
completion of this addition, stirring was continued for three hours at 20-25° C. The product precipitated during the first 20 minutes of this hold period. The product slurry was then quenched with 2500 ml of ice-cold water. The product was filtered, washed successively with water, 0.5% sodium
bicarbonate solution, and finally with two more water washes, and dried under vacuum. This procedure produced 1037.1 g of 2-(2-Bromo-2-nitroethenyl) furan (95.1% yield), assaying 99.4% by GC. TABLE I
2- ( 2-Bromo-2-Nitroethenyl ) Furan (BNEF )
Schiff Base
formed
prior to Solvent BNEF
Ex . Bromonitromethane for Yield, Assay
No. BuNH2 Addition Condensation % %
1 10 mol% No MeOH 25-39 89.0
2 10 mo1% No HOAc 66.3 98.4
3 Stoich. No MeOH Tar
4 Stoich. Yes HOAc 89.4 96.5
5 Stoich. Yes HOAc 93.9 99.4

Claims

What is claimed is:
1. A process for preparing 2-(2-bromo-2-nitroethenyl) furan which comprises the steps of:
a. converting furfural to a Schiff base in an organic solvent, said converting comprising reacting the furfural with a primary amine, said reacting yielding the Schiff base and water;
b. isolating the Schiff base by removing the organic solvent from the Schiff base;
c. dissolving the Schiff base in a polar,
water-miscible solvent;
d. reacting the Schiff base solution of step c with bromonitromethane to form a reaction mixture including
2-(2-bromo-2-nitroethenyl) furan; and
e. isolating the 2-(2-bromo-2-nitroethenyl) furan product from the reaction mixture.
2. The process of claim 1 in which the primary amine is a primary aliphatic amine.
3. The process of claim 2 in which the primary amine is n-butylamine.
4. The process of claim 1 in which step c comprises dissolving the Schiff base in acetic acid.
5. The process of claim 1 in which step b comprises removing the organic solvent and water from the Schiff base.
6. The process of claim 5 in which the organic solvent forms an azeotrope with water, and in which step b comprises removal of the organic solvent and water by azeotropic distillation.
7. The process of claim 6 in which step c comprises dissolving the Schiff base in acetic acid.
8. The process of claim 7 in which the primary amine is n-butylamine.
9. The process of claim 8 in which step e comprises quenching the reaction mixture of step d with water to precipitate the 2-(2-Bromo-2-nitroethenyl) furan product.
10. The process of claim 1 in which the organic solvent of step a. is selected from the group consisting of
cyclohexane, methylcyclohexane, methylene dichloride,
ethylene dichloride, chloroform, benzene, toluene, o-xylene, m-xylene, p-xylene, and aliphatic alcohols selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl alcohols.
11. The process of claim 10 in which the organic solvent is selected from the group consisting of cyclohexane,
methylcyclohexane, toluene, methylene dichloride and
methanol.
12. The process of claim 10 in which the organic solvent of step a. is methanol.
13. The process of claim 1 in which the polar,
water-miscible solvent of step c. is a carboxylic acid.
14. The process of claim 13 in which the polar,
water-miscible solvent is selected from the group consisting of acetic acid and propionic acid.
15. The process of claim 14 in which the polar,
water-miscible solvent is acetic acid.
16. The process of claim 1 in which the primary amine of step a. is selected from the group consisting of aliphatic primary amines and aromatic primary amines.
17. The process of claim 16 in which the primary amine of step a. is selected from the group consisting of C1-C8 primary aliphatic amines, primary arylalkylamines and
aromatic primary amines.
18. The process of claim 17 in which the primary amine is a primary aliphatic amine selected from the group
consisting of methylamine, ethylamine, n-propylamine,
i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-amylamine, t-amylamine, 1-methylbutylamine and
2-methylbutylamine.
19. The process of claim 18 in which the primary amine is selected from the group consisting of ethylamine,
n-propylamine, n-butylamine and n-amylamine.
20. The process of claim 19 in which the primary amine is n-butylamine.
21. The process of claim 17 in which the primary amine is a primary arylalkylamine selected from the group
consisting of benzylamine, chlorobenzylamine and
methylbenzylamine.
22. The process of claim 17 in which the primary amine is an aromatic primary amine selected from the group
consisting of aniline, toluidine, p-chloroaniline and
xylidene.
23. The process of claim 17 in which the primary amine is selected from the group consisting of methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-amylamine, t-amylamine,
1-methylbutylamine, 2-methylbutylamine, benzylamine,
chlorobenzylamine, methylbenzylamine, aniline, toluidine, p-chloroaniline and xylidene.
24. The process of claim 1 in which:
the organic solvent of step a. is selected from the group consisting of cyclohexane, methylcyclohexane, methylene dichloride, ethylene dichloride, chloroform, benzene, toluene, o-xylene, m-xylene, p-xylene, and aliphatic alcohols selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and t-butyl alcohols;
the polar, water-miscible solvent is selected from the group consisting of acetic acid and propionic acid; and
the primary amine is selected from the group consisting of methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, n-amylamine, t-amylamine, 1-methylbutylamine, 2-methylbutylamine,
benzylamine, chlorobenzylamine, methylbenzylamineaniline, toluidine, p-chloroaniline and xylidene.
25. The process of claim 24 in which the organic solvent is methanol, the polar, water-miscible solvent is acetic acid, and the primary amine is n-butylamine.
PCT/US1991/009018 1990-12-03 1991-12-03 Process for the preparation of 2-(2-bromo-2-nitroethenyl)furan Ceased WO1992009591A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE69122882T DE69122882T2 (en) 1990-12-03 1991-12-03 METHOD FOR PRODUCING 2- (2-BROMO-2-NITROETHENYL) FURAN
KR1019930701650A KR930703280A (en) 1990-12-03 1991-12-03 Method for preparing 2- (2-bromo-2-nitroethenyl) furan
EP92902359A EP0561994B1 (en) 1990-12-03 1991-12-03 Process for the preparation of 2-(2-bromo-2-nitroethenyl)furan
JP4502684A JPH06503575A (en) 1990-12-03 1991-12-03 Method for producing 2-(2-bromo-2-nitroethenyl)furan
AU91181/91A AU648628B2 (en) 1990-12-03 1991-12-03 Process for the preparation of 2-(2-bromo-2-nitroethenyl)furan
FI932507A FI101792B1 (en) 1990-12-03 1993-06-02 Process for the preparation of 2- (2-bromo-2-nitroethenyl) furan
NO932013A NO301761B1 (en) 1990-12-03 1993-06-02 Process for the preparation of 2- (2-bromo-2-nitroethenyl) furan

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US621,339 1984-06-15
US62133990A 1990-12-03 1990-12-03
US686,427 1991-04-16
US07/686,427 US5138076A (en) 1990-12-03 1991-04-16 Process for the preparation of 2-(2-bromo-2-nitroethenyl)furan

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CA (1) CA2056665A1 (en)
DE (1) DE69122882T2 (en)
FI (1) FI101792B1 (en)
IE (1) IE62681B1 (en)
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Citations (1)

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WO1989011793A1 (en) * 1988-06-10 1989-12-14 Great Lakes Chemical Corporation A new industrial antimicrobial: uses for 2-(2-bromo-2-nitroethenyl)-furan and a new process of forming 2-(2-bromo-2-nitroethenyl)-furan

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989011793A1 (en) * 1988-06-10 1989-12-14 Great Lakes Chemical Corporation A new industrial antimicrobial: uses for 2-(2-bromo-2-nitroethenyl)-furan and a new process of forming 2-(2-bromo-2-nitroethenyl)-furan

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IE62681B1 (en) 1995-02-22
EP0561994A1 (en) 1993-09-29
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DE69122882D1 (en) 1996-11-28
ATE144505T1 (en) 1996-11-15
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IL100186A0 (en) 1992-08-18
NO932013L (en) 1993-06-02
JPH06503575A (en) 1994-04-21
EP0561994B1 (en) 1996-10-23
AU648628B2 (en) 1994-04-28
FI101792B1 (en) 1998-08-31
NO301761B1 (en) 1997-12-08
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FI932507L (en) 1993-06-02
IL100186A (en) 1996-10-16

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