CA1120059A - Process for preparing n-ethylethylenediamine - Google Patents
Process for preparing n-ethylethylenediamineInfo
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- CA1120059A CA1120059A CA000318858A CA318858A CA1120059A CA 1120059 A CA1120059 A CA 1120059A CA 000318858 A CA000318858 A CA 000318858A CA 318858 A CA318858 A CA 318858A CA 1120059 A CA1120059 A CA 1120059A
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- eda
- weight
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- heptane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/08—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
Abstract
ABSTRACT
This disclosure describes a novel process for preparing N-ethylethylenediamine which is useful as an intermediate for purifying penicillin. N-Ethylethylenediamine is also useful for manufacturing piperacillin. Piperacillin is useful as an anti-biotic. More particularly, the invention relates to a process for the efficient reaction of an ethyl halide and ethylenediamine and the recovery of anhydrous, ethylenediamine-free N-ethylethyl--enediamine therefrom.
This disclosure describes a novel process for preparing N-ethylethylenediamine which is useful as an intermediate for purifying penicillin. N-Ethylethylenediamine is also useful for manufacturing piperacillin. Piperacillin is useful as an anti-biotic. More particularly, the invention relates to a process for the efficient reaction of an ethyl halide and ethylenediamine and the recovery of anhydrous, ethylenediamine-free N-ethylethyl--enediamine therefrom.
Description
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In the present invention, there is provided a process for preparing N-ethylethylenediamine H
C2H5~CH2CH2NH2 (hereafter referred to as NEED) wherein an ethyl halide is reacted with ethylenediamine (hereafter referred to as EDA) at a temperature of from about -10C to about 120C. and at a mole ratio of EDA to said ethyl halide of about 1-20:1, in the presence of about 0-50% by weight of water, to form a reaction mixture containing NEED. The resulting reaction rmxture is then contacted with an aqueous alkalizing agent to form a liquid two-phase mixture consisting of an organic layer and an aIkalized aqueous layer and the alkaliz-ed aqueous layer is separated. The organic layer is diluted with about 0.2-100% by weight of a suitable aliphatic hydrocarbon solvent and the resulting mlxture is azeotropically fractionally distilled to remove all the water and unreacted EDA therefrom. The resulting reaction mixture is then fractionally distilled to remove residual hydrocarbon solvent and recover NEED in a purity greater than about 99%.
In one aspect, the present invention provides a process for prepar-ing N-ethylethylenediamine (NEED) comprising reacting ethylenediamine (EDA) and an bth~l halide at a mole ratio of EDA to said ethyl halide of about 1-20:1 and a tem~erature of from about -lo&. to about 120C in the presence of about 0-50% by wei~ht of water to obtain an aIkylation reaction mixture;
neutralizing said reaction mixture by contacting with an aqueous solution containing about 1 - 2 molecular equivalents of an inorganic aIkalizing agent based on the ethyl halide; separating the aqueous layer ~rom the neutralized organic layer and adding to said organic layer about 0.2-100%
by weight, based on the weight of said organic layer, of a suitable aliphatic hydrocarbon solvent selected from the group consisting of n-heptane, iso-octane, cyclohexane, n-hexane, methylcyclohexane, and _-pentane; azeotropical-ly fractionally distilling all water and EDA from the resulting mixture;
and fractionally distilling the resulting reaction mixture to remove residual hydrocarbon solvent and recover NEED in a purity greater than about
In the present invention, there is provided a process for preparing N-ethylethylenediamine H
C2H5~CH2CH2NH2 (hereafter referred to as NEED) wherein an ethyl halide is reacted with ethylenediamine (hereafter referred to as EDA) at a temperature of from about -10C to about 120C. and at a mole ratio of EDA to said ethyl halide of about 1-20:1, in the presence of about 0-50% by weight of water, to form a reaction mixture containing NEED. The resulting reaction rmxture is then contacted with an aqueous alkalizing agent to form a liquid two-phase mixture consisting of an organic layer and an aIkalized aqueous layer and the alkaliz-ed aqueous layer is separated. The organic layer is diluted with about 0.2-100% by weight of a suitable aliphatic hydrocarbon solvent and the resulting mlxture is azeotropically fractionally distilled to remove all the water and unreacted EDA therefrom. The resulting reaction mixture is then fractionally distilled to remove residual hydrocarbon solvent and recover NEED in a purity greater than about 99%.
In one aspect, the present invention provides a process for prepar-ing N-ethylethylenediamine (NEED) comprising reacting ethylenediamine (EDA) and an bth~l halide at a mole ratio of EDA to said ethyl halide of about 1-20:1 and a tem~erature of from about -lo&. to about 120C in the presence of about 0-50% by wei~ht of water to obtain an aIkylation reaction mixture;
neutralizing said reaction mixture by contacting with an aqueous solution containing about 1 - 2 molecular equivalents of an inorganic aIkalizing agent based on the ethyl halide; separating the aqueous layer ~rom the neutralized organic layer and adding to said organic layer about 0.2-100%
by weight, based on the weight of said organic layer, of a suitable aliphatic hydrocarbon solvent selected from the group consisting of n-heptane, iso-octane, cyclohexane, n-hexane, methylcyclohexane, and _-pentane; azeotropical-ly fractionally distilling all water and EDA from the resulting mixture;
and fractionally distilling the resulting reaction mixture to remove residual hydrocarbon solvent and recover NEED in a purity greater than about
- 2 -.,j ~ .
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99% .
Preferably the reaction between the ethyl halide and the EDA
is carried out at about 25 - 50C in the presence of about 15 - 30% by weight of water and at a mole ratio of ED~ to ethyl halide of about 2-5:1.
me resulting reaction mixture is then contacted with aqueous caustic soda and the organic layer is diluted with about 0.2-20% by weight of the ali-phatic hydrocarbon solvent before carrying out the distillation.
The process of the subject invention can be mcdified by the addi.tional steps of: (1) recovering and recycling aqueous EDA from the azeotroper (2) recovering and recycling the aliphatic hydrocarbon solvent, and (3) contacting the separated, alkalized aqueous layer with about 10 -100% by weight of said hydrocarbon - 2a -~L~Z~
solvent based on the weight of said organic layer, separating the extracted aqueous layer and diluting the organic layer with the hydrocarbon extract before proceeding with the azeotropic frac-tional distillation.
The present invention also provides processes for the removal of water and/or EDA from NEED by addiny a suitable ali-phatic hydrocarbon solvent thereto, azeotropically fractionally distilling the water and/or EDA therefrom, and fractionally dis-tilling to remove residual hydrocarbon solvent and recover anhy-drous and/or ~DA-free, NEED. The advantages of the process of the present invention over previously available processes are that (1) the final product ha~ a purity greater than about 99%; and (2~ the process results in high yields and high productivity~
In accordance with the present invention there is also provided an alternative process for preparing NEED of about 99~
purity comprising (a) reacting an ethyl halid~ and EDA at a mole ratio of EDA to said ethyl halide of about 1-20:1, and a tempera-ure of about -10C to about 120C under anhydrous conditions to obtain an alkylation reaction mixture; (b) adding thereto about - 20 0~2-30% by weight of a suitable aliphatic hydrocarbon solvent, based on the weight of said alkylation reaction mixture; (c) frac-tionally distllling a mixture of EDA and said aliphatic hydrocarbon solvent therefrom to essentially remove EDA from the resulting mix-ture; (d) neutralizing the resulting reaction mixture by contact-ing it with at least 0.9 molecular equivalent of a suitable alka-lizing agent per mole of said ethyl halide to form a slurry of an alkali halide precipitate; (e) separating said alkali halide from -said slurry and recovering the resulting mother liquor therefrom;
' (f),,washing said separated alkali halide with said aliphatic hydro-carbon solvent; (g) fractionally distilling a combination of said mother liquor from step (e) plus recovered aliphatic hydrocarbon wash liquor from step (f) to remove essentially all water and re-sidual EDA from the resulting mixture; and (h) fractionally dis-tilling ~he resulting reaction mixture to remove residual ali-phatic hydrocarbon solvent and recover said NEED.
EDA, either as an anhydrous liquid or containing water, and an ethyl halide, preferably ethyl chloride, are admix~d in a suitable reactor vessel while agitating and maintaining the reac-tion mixture at from about -10C to about 120C. (preferably at about 25-50C), over a period of about 5-15 hours (preferably about 7-9 hours) t to provide a mole ratio of EDA to ethyl halide of about 1-20:1 (preferably about 2-5:1) and form a reaction mix-ture containing about 0-50% by weight of water (preferably about 15-30%). Suitable ethyl halides include ethyl chloride, ethyl bromide and ethyl iodide. The total residence time in the reactor vessel depends on the temperature employed, with shorter residence times employed with higher temperatures.
The reaction mixture is then vi~orously contacted with an aqueous solution of an alkalizing agent to form a two-phase liquid mixture, consisting of an organic layer and an alkalized aq~eous layer. Sufficient alkalizing agent is employed so $hat the p~ of the aqueous layer does not go below about 7, preferably not below 8. Suitable alkalizing agents include sodium and pot-assium hydroxide, either singly or in mixtures. The preferred alkalizing agent is about 50% aqueous sodium hydroxide.
After allowing the two-phaæe mixture to settle, the aqueous layer is separdt~d therefrom to obtain an organic layer containing NEED, unreacted EDA, and higher alkylation products such as N,N'-diethylethylenediamine, N,N-diethylethylenediamine, N,N,N'-triethylethylenediamine, and N,N,NI,N'tetraethylethylenedi-amine. The aqueous layer generally contains about 1-3~ EDA and about 0.5-1% NEED. The organic layer is then diluted with about :,, 10-100% by weight, preferably about 10-20% by weight, of a suit-able aliphatic hydrocarbon solvent, based on the ~7eight of said organic layer.
Preferably, the separated aqueous layer is extracted with about 10-100~ by weight, preferably about 10-20% by weight, oE said suitable aliphatic hydrocarbon solvent, based on the weight of said organic layer and the two-phase mixture is allowed to settle. The extracted aqueous layer is then sepa-rated and the hydrocarbon solvent extract is used to dilute the above mentioned organic layer.
As employed herein, the term "suitable aliphatic hydro-carbon solvent" is defined as an aliphatic hydrocarbon solvent which is miscible with NEED, immi~cible with EDA, and which azeo-tropes with water and/or EDA below about 128~C. to about 131C.
without inclusion of substantial amounts of NEED. Suitable ali-phatic hydrocarbon solvents include n-heptane, sooctane/ cyclo-hexane, n-hexane, methylcyclohexanel n-pentane, and the like, al-though the preferred aliphatic hydrocarbon solvent is n-heptane.
Aromatic hydrocarbons cannot be used instead of aliphatic hydro-carbons because they are miscible with both EDA and NEED.
The diluted organic layer is then heated to boiling through a distillation column to azeotropically fractionally dis-till off any residual EDA and water. After allowing the distil-late to settle, the lower EDA-water layer may be separated and recycled to the alkylation vessel, and the upper hydrocarbon layer may be recycled to the distillation vessel until anhydrous EDA-free NEED is obtained, or transferred to a vessel for extraction of the original two-phase mixture.
The residual EDA-free reaction mixture, containing NEED, higher alkylated ethylenediamines, and the aliphatic s~
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hydrocarbon solvent is now fractionally distilled, using a fractionation column containing sufficient theoretical plates, to separate said aliphatic hydrocarbon solvent from NEED. -For example, using a column containing 15 theoretical plates and n-heptane as the solvent, the n-heptane distills off as a forerun boilingat about 98-100C. The forerun of hydrocarbon solvent so obt~ined may be recycled to other stagesof the process, such as dilution of the organic layer, azeotroping, EDA and water from the reaction mixture, or extracting the aqueous layer, as described above.
After removal of the Eorerun of hydrocarbon solvent, the distillation ls continued to obtain NEED (b.p. 130-131C, purity greater than 99%) in a yield of about 63-65~ based on the ethyl halide charged. The procedure employed herein may also be used to remove water and/or EDA from NEED by adding a suitable amount of said hydrocarbon solvent thereto, azeo-tropically frac~ionally distilling water or EDA, or both, therefrom and fractionally distilling the residue to remove excess hydro-carbon solvent and obtain anhydrous, EDA-free NEED. It is to be understood that the aforedescribed process may also be carried out continuously using appropriate vessels, such as cantinuous flow reactors, splitter vessels, distil-lation columns, and the like.
In the alternative pro oess ethylediamine as an anhy-drous liquid, is reacted with an ethyl halide as shown belcw H
C2H5X ~ H2N-VH2CH2-NH2-----------~ C2H5 C 2 2 2 wherein X is a halo atom, such as chloro, bro~o, fluoro, or ido, preferably chloro. The reaction is carried out while agitating the reaction mixture in a suitable reactor vessel at about -10C
~ZO~)~9 to about 120C, preferably at about ~5-75C, over a period of about 1-24 hours, preferably about 2-6 hours. The mole ratio of EDA to ethyl halide employed is about 1-20 to 1, preferably about 2-5 to 1. The total residence time in the reactor vessel will de-pend on the temperature employed, with shorter residence times em-ployed with higher temperatures.
Upon completion of the reaction, the reaction mixture is diluted with about 0.2-30% by weight, preferably about 0.5-1.0~ by weight, of a suitable aliphatic hydrocarbon solvent, based on the weight of the reaction mixture. As employed herein the term "suitable aliphatic hydrocarbon solvent" has the same mean-i~g as previously defined. The diluted reaction mixture is then heated to boiling through a distillation column to azeotropically fractionally distill of~ any residual EDA. Optionally, the EDA
distilla~e may be reco~ered and recycled.
~ ~ Suitable aliphatic hydrocarbon solvents include n-heptane isooctane, cyclohexane, n-hexane, methylcyclohexane, n-pentane, and the like, although the preferred aliphatic hydrocarbon sol-vent is n-heptane.
The reaction mixture is then neutralized by contacting it with at least 0.9 molecular equivalent of a suitable alkali-zing agent per mole of alkyl halide us~d. As employed herein the term "suitable alkalizing agent" is defined as sodium or potas-sium hydroxide, either singly or in mixtures. The pre~erred al~a-~5 lizing agent is 50% aqueous sodium hydroxide.
The resulting alkali halide precipitate is sep~rated from the resulting slurry by conventional means, such as filtra-tion or centrifugation, and washed with the aliphatic hydrocarbon solvent described previously, preferably with n-heptane.
The aliphatic hydrocarbon solvent wash liquors are col-~LlZ0~5~9 lected and combined with the mother liquor obtained by the sepa-ration of the alkali halide precipitate from the slurry formed by the addition of an alkalizing agent to the reaction mixture.
The eombined liquors are azeotropically fractionally distilled at atmospheric pressure through a packed column, preferably with recycle of heptane distillate to the top of the column, until the residual material is essential]y free of EDA and water.
The resulting essentially EDA-free reaction mixture, eontaining the produet NEED, higher alkylated ethylenediamines, and the aliphatic hydrocarbon solvent is now fractionally distil-led, using a fractionation column containing sufficient theoret-ical plates, to separate said aliphatic hydrocarbon solvent from the product NEED. For example, using a column containing 15 theo-retical plates, n-heptane distills off as a forerun boiling at about 98-100C. The forerun of hydrocarbon solvent so ob-tained may be reeycled to other stages of the process, such as dilution of the reaction mixture, or azeotroping ED~ or water from the reaction mixture.
After removal o~ the forerun of hydrocarbon solvent the reaction mixture is preferably clarified to remove any insol-ubles and distillation of the clarified solution is continued to obtain NEED (b.p. 130-131C) in a purity greater than 99% and a yield of about 62-65% of theoretical based on the ethyl halide charged.
It is to be understood that the aforedescribed process may also be earried out continuously using appropriate vessels, sueh as continuous flow reactors, separation vessels, distilla-tion columns, and the like.
The following examples are provided to illustrate 0 the invention. Except as otherwise noted, all parts are by - ~,'h~
weight and all ranges are inclusive of both numbers. The purity of the product is expressed as area percent, as determined by vapor phase chromatography (VPC).
Example 1 This example illustrates the use of anhydrous EDA.
Ethyl chloride (565 grams; 8.76 moles) is added to an-hydrous EDA (1420 grams; 23.63 moles) at 30-40C over a period of 5 hours. The reaction mixture is stirred for 2 hours after the addition is completed and 50% caustic soda (935 ml; 17.5 moles) is added thereto. The resulting two-phase mixture is stir-red for 30 minutes, allowed to settle, and the aqueous phase is separated and extracted twice with 150 ml. of n-heptane. The hep-tane extracts are added to the organic phase and the combined solution is heated to azeotropically distill water and EDA there-from at 33-97C., using a fractionation column and a splitter device to return distilled heptane to the distillation vessel and to separate the denser aqueous EDA phase. In this ~anner an aqueous EDA phase is separated consisting of 394 grams of water and 896 grams of EDA (14.91 moles). The EDA~free residue is fractionally distilled to obtain a heptane forerun (b.p. 98~-102C.) containing 3-4% by weight of NEED, and 484 grams of NEED ~b.p.
130-131C.) of greater than 99.8% purity by VPC~ The yield is 62.7~ of theoretical based on ethyl chloride.
Example 2 This_example illustrates the_u~e of recovered aqueous EDA
Ethyl chloride (545 grams; 8.45 moles) is added at 30-40C. over a period of 5 hours to a mixture of 1245 grams of aque-ous eda recovered from Example 1 (containing 14.39 moles of EDA) and anhydrous EDA (555 grams; 9,23 moles). The reaction mixture is stirred or 2 hours after the addition is completed and 50~
_ g _ ~ ~'Z O ~ 3 9 caustic soda (902 ml; 16.9 moles) is added thereto. The resulting two-phase mixture is processed as described in Example 1 utilizing recovered n-heptane from Example 1 to extract the separated aque-ous phase. Fractional distillation of the EDA-free residual material yields a heptane forerun containing 3-4% by weight of NEED, and 483 grams of NEED (b.p. 130-131C) of greater than 99.8~ purit~ by VPC. The yield is 65% of theoretical based on ethyl chloride.
EX~MPLE 3 This example illustrates the separation of EDA from NEED by azeotropic distillation.
A mixture of EDA (500 grams) and NEED (500 grams) is diluted with 200 ml. of n-heptane and heated to azeotropically fractionally distill (b.p. 87-90C) EDA therefrom, using a dis-tillation column and a device which returns -the recovered heptane to the distillation apparatus and allows for the recovery of the denser EDA phase. The EDA thus recovered contains less than 1%
ME$D by VPC. The EDA-free residue is then fractionally distil- ~;
led to recover a heptane forerun and pure NEED (b.p. 130 131 C).
In the manner described above, substituting cyclo-hexane, _-hexane, or isooctane for the n-heptane, similar resul-ts are obtained.
EXAMPLE _ This example illustrates the separation of water for NEED by azeotropic distillation.
To a mixture of 56 grams of NEED and 10 grams of water is added 50 ml. of n-heptane. The mixture is heated to boiling and the water is azeotropically fractionated (b.p. 88-98&) therefrom using a distillation column and a splitter appa~
ratus which returns the recovered heptane to the distillation '~"' `` '' r~9 apparatus and allows for the removal of the denser water phase.
After removal of the water is complete, the residue is fractionally distilled to recover a heptane ~orerun and NEED (b.p. 130-131~C) containing less than 0.2% water by VPC.
In the manner described above, substituting cyclo-hexane, n-hexane, or lsooctane for the n-heptane, similar results are obtained.
Ethyl chloride t62.4 grams; 0.967 mole) ls added to stirred ethylenediamine (146.3 grams; 2.43 moles) over a period of 1 hour while allowing the temperature to rise to 95C. Upon completion of the addition of the ethyl chloride, n-heptane (34.2 grams) is added thereto and the resulting mixture is azeotropical-ly distilled using a fractionatlon column and a Dean-Stark device to collect the two-phase liquid distillate consisting of a lower layer of ethylenediamine (85.09 grams) and an upper layer of hep-tane which is recycled back to the fractionation column until all of the ethylenediamine is removed therefrom.
The remaining material is cooled to 80~C, neutralized with 50% aqueous sodium hydroxide (77.36 grams; 0O967 mole) and the resulting precipitate of sodium chloride is separated by fil-tration to obtain a filter cake and a two-phase liquid filtrate.
The filter cake is then washed with heptane (50 mls) and the wash-ing is added to the original two-phase filtrate.
The resulting two-phase liquid is then azeotropically distilled using a fractionation column and a Dean-Stark device to collect the two-phase distillate consisting of n heptane and water.
After all of the water is removed the residue is fractionally distilled to remove any heptane and recover N-ethylethylenediamine (54.5 grams; b.p. 130-131~C, 64% of theoretical) in a purity of 99%.
EX~MPLE 6 The procedure of Example S is followed in every detail up to the point of the final distillation. After all the water is removed by azeotropic distillation the residual material is filtered to separate a white precipitate (4.32 grams). The filtex cake is then washed with heptane (16 gxams) and the wash-ing is combined with the filtrate. The combined filtrate plus washing is then fractionally distilled to remove heptane and re-cover N-ethylethylenediamine (53.7 grams; b.p. 130-131~C; 63% of theoretical) in 99% purity.
To a glass-lined reactor is charged 848 parts of ethyl-enediamine (98%) followed by 331 parts of liquid ethyl chloride, charged through a dip leg at a rate to maintain the reaction lS mixture at 45-55C. The mixture is stirred for 2 hours and 91 parts of heptane are added thereto. The excess ethylenediamine is azeotropically distilled off through a packed column with re-cycle of the heptane distillate to the top of the column. A tot-al of 492 parts of ethylenediamine is recovered from the distil-late for recycle. The reaction mixture is neutralized with 402 parts of 50% caustic soda, cooled to room temperature, and cen-trifuged to remove the sodium chloride by-product. The salt cake is washed with 70 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined vessel. Water is azeo-tropically distilled off from the combined liquors through a pack-ed column with recycle of the distilled heptane to thP top of the column. After all of the water is removed the heptane is fxac-tionally distilled off through the packed column to obtain a resi-due containing 273 parts of N-ethylethylenediamine. This residue is reserved for subsequent combination with the residues of Ex-)Q~9 amples 8-10.
-To a glass-lined reactor is charged 492 parts of re-covered ethylenediamine from Example 7 and 375 parts of fresh ethylenediamine (98%). To this mixture is charged 331 parts of ethyl chloride at a rate to maintain the reaction mixture at 55-65C. The mixture is stirred for 2 hours and 45 parts of recov-ered heptane from Example 7 are added thereto. The excess ethyl-enediamine is azeotropically distilled off through a packed col~
umn with recycle of the heptane distillate to the top of the column. A total of 501 parts of ethylenediamine is recovered from the distillate for recycle. The reaction mixture is neutra-lized with 407 parts of 50% caustic soda, cooled to room tempera-ture, and centrifuged to remove the sodi~ chloride by-product.
The salt cake is washed with 78 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined ves-sel. Water i5 azeotropically distilled off from the combined liquors through a packed column with recycle of the distilled heptane to the top of the column. After all of the water is re-moved the heptane is fractionally distilled off through the pack-ed column to obtain a residue containing 288 parts of N-ethyleth-ylenediamine. This residue is xeserved for subsequent combination with the residues of Examples 7, 9 and 10.
To a glass-lined reactor is charged 501 parts of recov-ered ethylenediamine from Example 8 and 396 parts of fresh ethyl-enediamine (98%). To this mixture is charged 331 parts of ethyl chloride at a rate to maintain the reaction mixture at 65-75C.
The mixture is stirred fo~ 2 hours and 28 parts of recovered hep-tane from Example 8 are added thereto. The excess ethylenediamine z~
is azeotropically distilled off through a packed column with re-cycle of the heptane distillate to the top of the column. A tot-al of 504 parts of ethylenediamine is recovered from the distil-late for recycle. The reaction mixture is neutralized with 409 parts of 50% caustic soda, cooled to room temperature, and centri-fuged to remove the sodium chloride by-product. The salt cake is washed with 82 parts of heptane and the wash liquor is combined ~ith the mother liquor in a glass-lined vessel. Water is azeo-tropically distilled off from the combined liquors through a pack-ed column with recycle of the distilled heptane to the top of thecolumn. After all of the water is removed the heptane is frac-tionally distilled off through the packed column to obtain a re-sidue containing 310 parts of N-ethylethylenediamine. This resi-due is reserved for subsequent combination with the residues of Examples 7, 8 and 10.
EXA~PLE 10 To a glass-lined reactor is char~ed 504 parts of re-covered ethylenediamine from Example 9 and 388 parts of fresh ethylenediamine (98%). To this mixture is charged 331 parts o ethyl chloride at a rate to maintain the reaction mixture at 55-- 65C. The mixture is stirred for 2 hours and 30 parts of recov-ered heptane from E~ample 9 are added the~eto. The e~cess eth-ylenediamine is azeotropically distilled off through a packed column with recycle of the heptane distillate to the top of the colum~. A total of 523 parts of ethylenediamine is recover-ed from the distillate for recycle. The reaction mixture is neutralized with 409 parts of 50~ caustic soda, cooled to room temperature, and centrifuged to remo~e the sodium chloride b~-product. The salt cake is washed with 91 parts of heptanP and ~he wash liquor is combined with the mother liquor in a glass-lined ~ ~Z~05~
vessel. Water is azeotropically dis~illed off from the combined liquors through a packed column with recycle of the distilled heptane to the top of the column. After all of the water is re-moved the heptane is fractionally distilled off through the packed column to obtain a residue containing 317 parts of N-ethylethyl-enediamine which is combined with the residues of Examples 7, 8 and 9. The resulting material is fractionally distilled through a packed column at atmospheric pressure to obtain 1120 parts of N-ethylethylenediamine, b.p. 129-131C. The yield is 61.9% of theoretical based on ethyl chloride.
. ~
~z~
99% .
Preferably the reaction between the ethyl halide and the EDA
is carried out at about 25 - 50C in the presence of about 15 - 30% by weight of water and at a mole ratio of ED~ to ethyl halide of about 2-5:1.
me resulting reaction mixture is then contacted with aqueous caustic soda and the organic layer is diluted with about 0.2-20% by weight of the ali-phatic hydrocarbon solvent before carrying out the distillation.
The process of the subject invention can be mcdified by the addi.tional steps of: (1) recovering and recycling aqueous EDA from the azeotroper (2) recovering and recycling the aliphatic hydrocarbon solvent, and (3) contacting the separated, alkalized aqueous layer with about 10 -100% by weight of said hydrocarbon - 2a -~L~Z~
solvent based on the weight of said organic layer, separating the extracted aqueous layer and diluting the organic layer with the hydrocarbon extract before proceeding with the azeotropic frac-tional distillation.
The present invention also provides processes for the removal of water and/or EDA from NEED by addiny a suitable ali-phatic hydrocarbon solvent thereto, azeotropically fractionally distilling the water and/or EDA therefrom, and fractionally dis-tilling to remove residual hydrocarbon solvent and recover anhy-drous and/or ~DA-free, NEED. The advantages of the process of the present invention over previously available processes are that (1) the final product ha~ a purity greater than about 99%; and (2~ the process results in high yields and high productivity~
In accordance with the present invention there is also provided an alternative process for preparing NEED of about 99~
purity comprising (a) reacting an ethyl halid~ and EDA at a mole ratio of EDA to said ethyl halide of about 1-20:1, and a tempera-ure of about -10C to about 120C under anhydrous conditions to obtain an alkylation reaction mixture; (b) adding thereto about - 20 0~2-30% by weight of a suitable aliphatic hydrocarbon solvent, based on the weight of said alkylation reaction mixture; (c) frac-tionally distllling a mixture of EDA and said aliphatic hydrocarbon solvent therefrom to essentially remove EDA from the resulting mix-ture; (d) neutralizing the resulting reaction mixture by contact-ing it with at least 0.9 molecular equivalent of a suitable alka-lizing agent per mole of said ethyl halide to form a slurry of an alkali halide precipitate; (e) separating said alkali halide from -said slurry and recovering the resulting mother liquor therefrom;
' (f),,washing said separated alkali halide with said aliphatic hydro-carbon solvent; (g) fractionally distilling a combination of said mother liquor from step (e) plus recovered aliphatic hydrocarbon wash liquor from step (f) to remove essentially all water and re-sidual EDA from the resulting mixture; and (h) fractionally dis-tilling ~he resulting reaction mixture to remove residual ali-phatic hydrocarbon solvent and recover said NEED.
EDA, either as an anhydrous liquid or containing water, and an ethyl halide, preferably ethyl chloride, are admix~d in a suitable reactor vessel while agitating and maintaining the reac-tion mixture at from about -10C to about 120C. (preferably at about 25-50C), over a period of about 5-15 hours (preferably about 7-9 hours) t to provide a mole ratio of EDA to ethyl halide of about 1-20:1 (preferably about 2-5:1) and form a reaction mix-ture containing about 0-50% by weight of water (preferably about 15-30%). Suitable ethyl halides include ethyl chloride, ethyl bromide and ethyl iodide. The total residence time in the reactor vessel depends on the temperature employed, with shorter residence times employed with higher temperatures.
The reaction mixture is then vi~orously contacted with an aqueous solution of an alkalizing agent to form a two-phase liquid mixture, consisting of an organic layer and an alkalized aq~eous layer. Sufficient alkalizing agent is employed so $hat the p~ of the aqueous layer does not go below about 7, preferably not below 8. Suitable alkalizing agents include sodium and pot-assium hydroxide, either singly or in mixtures. The preferred alkalizing agent is about 50% aqueous sodium hydroxide.
After allowing the two-phaæe mixture to settle, the aqueous layer is separdt~d therefrom to obtain an organic layer containing NEED, unreacted EDA, and higher alkylation products such as N,N'-diethylethylenediamine, N,N-diethylethylenediamine, N,N,N'-triethylethylenediamine, and N,N,NI,N'tetraethylethylenedi-amine. The aqueous layer generally contains about 1-3~ EDA and about 0.5-1% NEED. The organic layer is then diluted with about :,, 10-100% by weight, preferably about 10-20% by weight, of a suit-able aliphatic hydrocarbon solvent, based on the ~7eight of said organic layer.
Preferably, the separated aqueous layer is extracted with about 10-100~ by weight, preferably about 10-20% by weight, oE said suitable aliphatic hydrocarbon solvent, based on the weight of said organic layer and the two-phase mixture is allowed to settle. The extracted aqueous layer is then sepa-rated and the hydrocarbon solvent extract is used to dilute the above mentioned organic layer.
As employed herein, the term "suitable aliphatic hydro-carbon solvent" is defined as an aliphatic hydrocarbon solvent which is miscible with NEED, immi~cible with EDA, and which azeo-tropes with water and/or EDA below about 128~C. to about 131C.
without inclusion of substantial amounts of NEED. Suitable ali-phatic hydrocarbon solvents include n-heptane, sooctane/ cyclo-hexane, n-hexane, methylcyclohexanel n-pentane, and the like, al-though the preferred aliphatic hydrocarbon solvent is n-heptane.
Aromatic hydrocarbons cannot be used instead of aliphatic hydro-carbons because they are miscible with both EDA and NEED.
The diluted organic layer is then heated to boiling through a distillation column to azeotropically fractionally dis-till off any residual EDA and water. After allowing the distil-late to settle, the lower EDA-water layer may be separated and recycled to the alkylation vessel, and the upper hydrocarbon layer may be recycled to the distillation vessel until anhydrous EDA-free NEED is obtained, or transferred to a vessel for extraction of the original two-phase mixture.
The residual EDA-free reaction mixture, containing NEED, higher alkylated ethylenediamines, and the aliphatic s~
\~
hydrocarbon solvent is now fractionally distilled, using a fractionation column containing sufficient theoretical plates, to separate said aliphatic hydrocarbon solvent from NEED. -For example, using a column containing 15 theoretical plates and n-heptane as the solvent, the n-heptane distills off as a forerun boilingat about 98-100C. The forerun of hydrocarbon solvent so obt~ined may be recycled to other stagesof the process, such as dilution of the organic layer, azeotroping, EDA and water from the reaction mixture, or extracting the aqueous layer, as described above.
After removal of the Eorerun of hydrocarbon solvent, the distillation ls continued to obtain NEED (b.p. 130-131C, purity greater than 99%) in a yield of about 63-65~ based on the ethyl halide charged. The procedure employed herein may also be used to remove water and/or EDA from NEED by adding a suitable amount of said hydrocarbon solvent thereto, azeo-tropically frac~ionally distilling water or EDA, or both, therefrom and fractionally distilling the residue to remove excess hydro-carbon solvent and obtain anhydrous, EDA-free NEED. It is to be understood that the aforedescribed process may also be carried out continuously using appropriate vessels, such as cantinuous flow reactors, splitter vessels, distil-lation columns, and the like.
In the alternative pro oess ethylediamine as an anhy-drous liquid, is reacted with an ethyl halide as shown belcw H
C2H5X ~ H2N-VH2CH2-NH2-----------~ C2H5 C 2 2 2 wherein X is a halo atom, such as chloro, bro~o, fluoro, or ido, preferably chloro. The reaction is carried out while agitating the reaction mixture in a suitable reactor vessel at about -10C
~ZO~)~9 to about 120C, preferably at about ~5-75C, over a period of about 1-24 hours, preferably about 2-6 hours. The mole ratio of EDA to ethyl halide employed is about 1-20 to 1, preferably about 2-5 to 1. The total residence time in the reactor vessel will de-pend on the temperature employed, with shorter residence times em-ployed with higher temperatures.
Upon completion of the reaction, the reaction mixture is diluted with about 0.2-30% by weight, preferably about 0.5-1.0~ by weight, of a suitable aliphatic hydrocarbon solvent, based on the weight of the reaction mixture. As employed herein the term "suitable aliphatic hydrocarbon solvent" has the same mean-i~g as previously defined. The diluted reaction mixture is then heated to boiling through a distillation column to azeotropically fractionally distill of~ any residual EDA. Optionally, the EDA
distilla~e may be reco~ered and recycled.
~ ~ Suitable aliphatic hydrocarbon solvents include n-heptane isooctane, cyclohexane, n-hexane, methylcyclohexane, n-pentane, and the like, although the preferred aliphatic hydrocarbon sol-vent is n-heptane.
The reaction mixture is then neutralized by contacting it with at least 0.9 molecular equivalent of a suitable alkali-zing agent per mole of alkyl halide us~d. As employed herein the term "suitable alkalizing agent" is defined as sodium or potas-sium hydroxide, either singly or in mixtures. The pre~erred al~a-~5 lizing agent is 50% aqueous sodium hydroxide.
The resulting alkali halide precipitate is sep~rated from the resulting slurry by conventional means, such as filtra-tion or centrifugation, and washed with the aliphatic hydrocarbon solvent described previously, preferably with n-heptane.
The aliphatic hydrocarbon solvent wash liquors are col-~LlZ0~5~9 lected and combined with the mother liquor obtained by the sepa-ration of the alkali halide precipitate from the slurry formed by the addition of an alkalizing agent to the reaction mixture.
The eombined liquors are azeotropically fractionally distilled at atmospheric pressure through a packed column, preferably with recycle of heptane distillate to the top of the column, until the residual material is essential]y free of EDA and water.
The resulting essentially EDA-free reaction mixture, eontaining the produet NEED, higher alkylated ethylenediamines, and the aliphatic hydrocarbon solvent is now fractionally distil-led, using a fractionation column containing sufficient theoret-ical plates, to separate said aliphatic hydrocarbon solvent from the product NEED. For example, using a column containing 15 theo-retical plates, n-heptane distills off as a forerun boiling at about 98-100C. The forerun of hydrocarbon solvent so ob-tained may be reeycled to other stages of the process, such as dilution of the reaction mixture, or azeotroping ED~ or water from the reaction mixture.
After removal o~ the forerun of hydrocarbon solvent the reaction mixture is preferably clarified to remove any insol-ubles and distillation of the clarified solution is continued to obtain NEED (b.p. 130-131C) in a purity greater than 99% and a yield of about 62-65% of theoretical based on the ethyl halide charged.
It is to be understood that the aforedescribed process may also be earried out continuously using appropriate vessels, sueh as continuous flow reactors, separation vessels, distilla-tion columns, and the like.
The following examples are provided to illustrate 0 the invention. Except as otherwise noted, all parts are by - ~,'h~
weight and all ranges are inclusive of both numbers. The purity of the product is expressed as area percent, as determined by vapor phase chromatography (VPC).
Example 1 This example illustrates the use of anhydrous EDA.
Ethyl chloride (565 grams; 8.76 moles) is added to an-hydrous EDA (1420 grams; 23.63 moles) at 30-40C over a period of 5 hours. The reaction mixture is stirred for 2 hours after the addition is completed and 50% caustic soda (935 ml; 17.5 moles) is added thereto. The resulting two-phase mixture is stir-red for 30 minutes, allowed to settle, and the aqueous phase is separated and extracted twice with 150 ml. of n-heptane. The hep-tane extracts are added to the organic phase and the combined solution is heated to azeotropically distill water and EDA there-from at 33-97C., using a fractionation column and a splitter device to return distilled heptane to the distillation vessel and to separate the denser aqueous EDA phase. In this ~anner an aqueous EDA phase is separated consisting of 394 grams of water and 896 grams of EDA (14.91 moles). The EDA~free residue is fractionally distilled to obtain a heptane forerun (b.p. 98~-102C.) containing 3-4% by weight of NEED, and 484 grams of NEED ~b.p.
130-131C.) of greater than 99.8% purity by VPC~ The yield is 62.7~ of theoretical based on ethyl chloride.
Example 2 This_example illustrates the_u~e of recovered aqueous EDA
Ethyl chloride (545 grams; 8.45 moles) is added at 30-40C. over a period of 5 hours to a mixture of 1245 grams of aque-ous eda recovered from Example 1 (containing 14.39 moles of EDA) and anhydrous EDA (555 grams; 9,23 moles). The reaction mixture is stirred or 2 hours after the addition is completed and 50~
_ g _ ~ ~'Z O ~ 3 9 caustic soda (902 ml; 16.9 moles) is added thereto. The resulting two-phase mixture is processed as described in Example 1 utilizing recovered n-heptane from Example 1 to extract the separated aque-ous phase. Fractional distillation of the EDA-free residual material yields a heptane forerun containing 3-4% by weight of NEED, and 483 grams of NEED (b.p. 130-131C) of greater than 99.8~ purit~ by VPC. The yield is 65% of theoretical based on ethyl chloride.
EX~MPLE 3 This example illustrates the separation of EDA from NEED by azeotropic distillation.
A mixture of EDA (500 grams) and NEED (500 grams) is diluted with 200 ml. of n-heptane and heated to azeotropically fractionally distill (b.p. 87-90C) EDA therefrom, using a dis-tillation column and a device which returns -the recovered heptane to the distillation apparatus and allows for the recovery of the denser EDA phase. The EDA thus recovered contains less than 1%
ME$D by VPC. The EDA-free residue is then fractionally distil- ~;
led to recover a heptane forerun and pure NEED (b.p. 130 131 C).
In the manner described above, substituting cyclo-hexane, _-hexane, or isooctane for the n-heptane, similar resul-ts are obtained.
EXAMPLE _ This example illustrates the separation of water for NEED by azeotropic distillation.
To a mixture of 56 grams of NEED and 10 grams of water is added 50 ml. of n-heptane. The mixture is heated to boiling and the water is azeotropically fractionated (b.p. 88-98&) therefrom using a distillation column and a splitter appa~
ratus which returns the recovered heptane to the distillation '~"' `` '' r~9 apparatus and allows for the removal of the denser water phase.
After removal of the water is complete, the residue is fractionally distilled to recover a heptane ~orerun and NEED (b.p. 130-131~C) containing less than 0.2% water by VPC.
In the manner described above, substituting cyclo-hexane, n-hexane, or lsooctane for the n-heptane, similar results are obtained.
Ethyl chloride t62.4 grams; 0.967 mole) ls added to stirred ethylenediamine (146.3 grams; 2.43 moles) over a period of 1 hour while allowing the temperature to rise to 95C. Upon completion of the addition of the ethyl chloride, n-heptane (34.2 grams) is added thereto and the resulting mixture is azeotropical-ly distilled using a fractionatlon column and a Dean-Stark device to collect the two-phase liquid distillate consisting of a lower layer of ethylenediamine (85.09 grams) and an upper layer of hep-tane which is recycled back to the fractionation column until all of the ethylenediamine is removed therefrom.
The remaining material is cooled to 80~C, neutralized with 50% aqueous sodium hydroxide (77.36 grams; 0O967 mole) and the resulting precipitate of sodium chloride is separated by fil-tration to obtain a filter cake and a two-phase liquid filtrate.
The filter cake is then washed with heptane (50 mls) and the wash-ing is added to the original two-phase filtrate.
The resulting two-phase liquid is then azeotropically distilled using a fractionation column and a Dean-Stark device to collect the two-phase distillate consisting of n heptane and water.
After all of the water is removed the residue is fractionally distilled to remove any heptane and recover N-ethylethylenediamine (54.5 grams; b.p. 130-131~C, 64% of theoretical) in a purity of 99%.
EX~MPLE 6 The procedure of Example S is followed in every detail up to the point of the final distillation. After all the water is removed by azeotropic distillation the residual material is filtered to separate a white precipitate (4.32 grams). The filtex cake is then washed with heptane (16 gxams) and the wash-ing is combined with the filtrate. The combined filtrate plus washing is then fractionally distilled to remove heptane and re-cover N-ethylethylenediamine (53.7 grams; b.p. 130-131~C; 63% of theoretical) in 99% purity.
To a glass-lined reactor is charged 848 parts of ethyl-enediamine (98%) followed by 331 parts of liquid ethyl chloride, charged through a dip leg at a rate to maintain the reaction lS mixture at 45-55C. The mixture is stirred for 2 hours and 91 parts of heptane are added thereto. The excess ethylenediamine is azeotropically distilled off through a packed column with re-cycle of the heptane distillate to the top of the column. A tot-al of 492 parts of ethylenediamine is recovered from the distil-late for recycle. The reaction mixture is neutralized with 402 parts of 50% caustic soda, cooled to room temperature, and cen-trifuged to remove the sodium chloride by-product. The salt cake is washed with 70 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined vessel. Water is azeo-tropically distilled off from the combined liquors through a pack-ed column with recycle of the distilled heptane to thP top of the column. After all of the water is removed the heptane is fxac-tionally distilled off through the packed column to obtain a resi-due containing 273 parts of N-ethylethylenediamine. This residue is reserved for subsequent combination with the residues of Ex-)Q~9 amples 8-10.
-To a glass-lined reactor is charged 492 parts of re-covered ethylenediamine from Example 7 and 375 parts of fresh ethylenediamine (98%). To this mixture is charged 331 parts of ethyl chloride at a rate to maintain the reaction mixture at 55-65C. The mixture is stirred for 2 hours and 45 parts of recov-ered heptane from Example 7 are added thereto. The excess ethyl-enediamine is azeotropically distilled off through a packed col~
umn with recycle of the heptane distillate to the top of the column. A total of 501 parts of ethylenediamine is recovered from the distillate for recycle. The reaction mixture is neutra-lized with 407 parts of 50% caustic soda, cooled to room tempera-ture, and centrifuged to remove the sodi~ chloride by-product.
The salt cake is washed with 78 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined ves-sel. Water i5 azeotropically distilled off from the combined liquors through a packed column with recycle of the distilled heptane to the top of the column. After all of the water is re-moved the heptane is fractionally distilled off through the pack-ed column to obtain a residue containing 288 parts of N-ethyleth-ylenediamine. This residue is xeserved for subsequent combination with the residues of Examples 7, 9 and 10.
To a glass-lined reactor is charged 501 parts of recov-ered ethylenediamine from Example 8 and 396 parts of fresh ethyl-enediamine (98%). To this mixture is charged 331 parts of ethyl chloride at a rate to maintain the reaction mixture at 65-75C.
The mixture is stirred fo~ 2 hours and 28 parts of recovered hep-tane from Example 8 are added thereto. The excess ethylenediamine z~
is azeotropically distilled off through a packed column with re-cycle of the heptane distillate to the top of the column. A tot-al of 504 parts of ethylenediamine is recovered from the distil-late for recycle. The reaction mixture is neutralized with 409 parts of 50% caustic soda, cooled to room temperature, and centri-fuged to remove the sodium chloride by-product. The salt cake is washed with 82 parts of heptane and the wash liquor is combined ~ith the mother liquor in a glass-lined vessel. Water is azeo-tropically distilled off from the combined liquors through a pack-ed column with recycle of the distilled heptane to the top of thecolumn. After all of the water is removed the heptane is frac-tionally distilled off through the packed column to obtain a re-sidue containing 310 parts of N-ethylethylenediamine. This resi-due is reserved for subsequent combination with the residues of Examples 7, 8 and 10.
EXA~PLE 10 To a glass-lined reactor is char~ed 504 parts of re-covered ethylenediamine from Example 9 and 388 parts of fresh ethylenediamine (98%). To this mixture is charged 331 parts o ethyl chloride at a rate to maintain the reaction mixture at 55-- 65C. The mixture is stirred for 2 hours and 30 parts of recov-ered heptane from E~ample 9 are added the~eto. The e~cess eth-ylenediamine is azeotropically distilled off through a packed column with recycle of the heptane distillate to the top of the colum~. A total of 523 parts of ethylenediamine is recover-ed from the distillate for recycle. The reaction mixture is neutralized with 409 parts of 50~ caustic soda, cooled to room temperature, and centrifuged to remo~e the sodium chloride b~-product. The salt cake is washed with 91 parts of heptanP and ~he wash liquor is combined with the mother liquor in a glass-lined ~ ~Z~05~
vessel. Water is azeotropically dis~illed off from the combined liquors through a packed column with recycle of the distilled heptane to the top of the column. After all of the water is re-moved the heptane is fractionally distilled off through the packed column to obtain a residue containing 317 parts of N-ethylethyl-enediamine which is combined with the residues of Examples 7, 8 and 9. The resulting material is fractionally distilled through a packed column at atmospheric pressure to obtain 1120 parts of N-ethylethylenediamine, b.p. 129-131C. The yield is 61.9% of theoretical based on ethyl chloride.
Claims (14)
1. A process for preparing N-ethylethylenediamine (NEED) comprising reacting ethylenediamine (EDA) and an ethyl halide at a mole ratio of EDA to said ethyl halide of about 1-20:1 and a temperature of from about -10°C. to about 120°C.
in the presence of about 0-50% by weight of water to obtain an alkylation reaction mixture; neutralizing said reaction mixture by contacting with an aqueous solution containing about 1-2 molecular equivalents of an inorganic alkalizing agent based on the ethyl halide; separating the aqueous layer from the neutralized organic layer and adding to said organic layer about 0.2-100% by weight, based on the weight of said organic layer, of a suitable aliphatic hydrocarbon solvent selected from the group consisting of n-heptane, isooctane, cyclohexane, n-hexane, methylcyclohexane, and n-pentane; azeotropically fractionally distilling all water and EDA from the resulting mixture; and fractionally distilling the resulting reaction mixture to remove residual hydrocarbon solvent and recover NEED in a purity greater than about 99%.
in the presence of about 0-50% by weight of water to obtain an alkylation reaction mixture; neutralizing said reaction mixture by contacting with an aqueous solution containing about 1-2 molecular equivalents of an inorganic alkalizing agent based on the ethyl halide; separating the aqueous layer from the neutralized organic layer and adding to said organic layer about 0.2-100% by weight, based on the weight of said organic layer, of a suitable aliphatic hydrocarbon solvent selected from the group consisting of n-heptane, isooctane, cyclohexane, n-hexane, methylcyclohexane, and n-pentane; azeotropically fractionally distilling all water and EDA from the resulting mixture; and fractionally distilling the resulting reaction mixture to remove residual hydrocarbon solvent and recover NEED in a purity greater than about 99%.
2. A process according to Claim 1 wherein said EDA
and ethyl halide are reacted at a mole ratio of EDA to said ethyl halide of about 2-5:1 and a temperature of about 25°-50°C
in the presence of about 15-30% by weight of water to obtain said alkylation reaction mixture; said reaction mixture is neutralized by contacting with aqueous caustic soda; and about 0.2-20% by weight of said aliphatic hydrocarbon is added to said organic layer.
and ethyl halide are reacted at a mole ratio of EDA to said ethyl halide of about 2-5:1 and a temperature of about 25°-50°C
in the presence of about 15-30% by weight of water to obtain said alkylation reaction mixture; said reaction mixture is neutralized by contacting with aqueous caustic soda; and about 0.2-20% by weight of said aliphatic hydrocarbon is added to said organic layer.
3. A process according to Claim 1 wherein said aliphatic hydrocarbon is n-heptane.
4. A process according to Claim 2 wherein said aliphatic hydrocarbon is n-heptane.
5. A process for the preparation of NEED accord-ing to Claim 1 including the additional steps of (a) recover-ing aqueous EDA from the azeotrope and recycling to react with said ethyl halide; and (b) recovering the hydrocarbon solvent from the forerun of the distillation of NEED and recycling to the distillation mixture.
6. A process according to Claim 1 with the addi-tional steps of contacting said aqueous layer with 10-100% by weight of said hydrocarbon solvent based on the weight of said organic layer; separating the extracted aqueous layer;
and adding the hydrocarbon extract to said organic layer be-fore proceeding with said azeotropic fractional distillation.
and adding the hydrocarbon extract to said organic layer be-fore proceeding with said azeotropic fractional distillation.
7. A process according to Claim 5 with the addi-tional steps of contacting said aqueous layer with 10-100% by weight of said recovered hydrocarbon solvent based on the weight of said organic layer; separating the extracted aqueous layer;
and adding the hydrocarbon extract to said organic layer before proceeding with said azeotropic fractional distillation.
and adding the hydrocarbon extract to said organic layer before proceeding with said azeotropic fractional distillation.
8. A process for preparing N-ethylethylenediamine (NEED) of about 99% purity comprising (a) reacting an ethyl halide and ethylenediamine (EDA) at a mole ratio of EDA to said ethyl halide of about 1-20 to 1, and at a temperature of about -10°C to about 120°C under anhydrous conditions to obtain an alkylation reaction mixture; (b) adding to said reaction mixture about 0.2-30% by weight of a suitable aliphatic hydro-carbon solvent selected from the group consisting of n-heptane, isooctane, cyclohexane, n-hexane, methylcyclohexane, and n-pentane based on the weight of said reaction mixture; (c) azeotropically fractionally distilling the EDA and said ali-phatic hydrocarbon solvent to essentially remove EDA; (d) neutralizing the resulting mixture by contacting it with at least 0.9 molecular equivalent of a suitable alkalizing agent, per mole of said ethyl halide, to form a slurry of an alkali halide precipitate; (e) separating said alkali halide precipitate from said slurry and recovering the resulting mother liquor; (f) washing said separated alkali halide with said aliphatic hydrocarbon solvent; (g) azeotropically frac-tionally distilling a combination of said mother liquor from step (e) plus recovered aliphatic hydrocarbon wash liquor from step (f) to remove essentially all water and residual EDA from the resulting mixture; and (h) fractionally distilling said resulting mixture to remove residual aliphatic hydro-carbon solvent and recover said NEED.
9. A process according to Claim 8 wherein said ali-phatic hydrocarbon is n-heptane.
10. A process according to Claim 8 wherein step (a) is at a temperature of about 25°C to about 75°C.
11. A process according to Claim 8 wherein in step (a) the mole ratio of EDA to said ethyl halide is about 2-5 to 1.
12. A process according to Claim 8 wherein said ali-phatic hydrocarbon in step (b) is added to about 0.5-1.0%
based on the weight of said reaction mixture.
based on the weight of said reaction mixture.
13. A process according to Claim 9 wherein said n-heptane in step (b) is added to about 0.5-1.0% based on the weight of said reaction mixture.
14. A process according to Claim 8 wherein the alka-lyzing agent of step (b) is about 50% aqueous sodium hydroxide.
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| US87345078A | 1978-01-30 | 1978-01-30 | |
| US873,450 | 1978-01-30 | ||
| US96097278A | 1978-11-15 | 1978-11-15 | |
| US960,972 | 1992-10-14 |
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| CA1120059A true CA1120059A (en) | 1982-03-16 |
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|---|---|---|---|
| CA000318858A Expired CA1120059A (en) | 1978-01-30 | 1978-12-29 | Process for preparing n-ethylethylenediamine |
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| AR (1) | AR223161A1 (en) |
| AT (1) | AT364345B (en) |
| AU (1) | AU523012B2 (en) |
| CA (1) | CA1120059A (en) |
| CH (1) | CH642616A5 (en) |
| DD (1) | DD141305A5 (en) |
| DE (1) | DE2900060A1 (en) |
| DK (1) | DK153541C (en) |
| ES (1) | ES477283A1 (en) |
| FI (1) | FI67207C (en) |
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| GB (1) | GB2013180B (en) |
| HU (1) | HU182922B (en) |
| IL (1) | IL56176A (en) |
| IT (1) | IT1116499B (en) |
| NL (1) | NL190159C (en) |
| SE (1) | SE446628B (en) |
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| CN102260175A (en) * | 2011-06-08 | 2011-11-30 | 浙江大学 | Method for synthesizing 2-aminoethyl(ethyl)amine |
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| DE2929841A1 (en) * | 1979-06-14 | 1980-12-18 | American Cyanamid Co | METHOD FOR PRODUCING N-ALKYLAETHYLENE DIAMINES |
| JP2501562B2 (en) * | 1986-07-18 | 1996-05-29 | 三井東圧化学株式会社 | Method for producing N, N ''-dialkylalkanediamines |
| KR100407428B1 (en) * | 1999-03-19 | 2003-11-28 | 미쯔이카가쿠 가부시기가이샤 | Novel process for the preparation of n,n'-dialkylalkanediamines |
| CN102816071B (en) * | 2012-08-25 | 2014-05-07 | 太原理工大学 | Synthesis method of N-ethyl ethylene diamine |
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| DE1130814B (en) * | 1959-12-03 | 1962-06-07 | Basf Ag | Process for the continuous dewatering of ethylene diamines |
| BE626346A (en) * | 1961-12-21 | |||
| GB1507379A (en) * | 1976-08-05 | 1978-04-12 | Bp Chem Int Ltd | Hydrocarbyl substituted polyamines |
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- 1978-12-18 FI FI783891A patent/FI67207C/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102260175A (en) * | 2011-06-08 | 2011-11-30 | 浙江大学 | Method for synthesizing 2-aminoethyl(ethyl)amine |
| CN102260175B (en) * | 2011-06-08 | 2013-11-20 | 浙江大学 | Method for synthesizing 2-aminoethyl(ethyl)amine |
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| Publication number | Publication date |
|---|---|
| HU182922B (en) | 1984-03-28 |
| FR2415618B1 (en) | 1983-09-09 |
| CH642616A5 (en) | 1984-04-30 |
| GB2013180A (en) | 1979-08-08 |
| NL7900746A (en) | 1979-08-01 |
| DK153541B (en) | 1988-07-25 |
| FI67207B (en) | 1984-10-31 |
| IT1116499B (en) | 1986-02-10 |
| FR2415618A1 (en) | 1979-08-24 |
| FI67207C (en) | 1985-02-11 |
| DE2900060C2 (en) | 1988-01-21 |
| AU4255078A (en) | 1979-08-09 |
| AT364345B (en) | 1981-10-12 |
| GB2013180B (en) | 1982-05-12 |
| NL190159C (en) | 1993-11-16 |
| DK153541C (en) | 1988-12-05 |
| IL56176A (en) | 1982-03-31 |
| NL190159B (en) | 1993-06-16 |
| AU523012B2 (en) | 1982-07-08 |
| DK36379A (en) | 1979-07-31 |
| AR223161A1 (en) | 1981-07-31 |
| IT7947792A0 (en) | 1979-01-26 |
| FI783891A (en) | 1979-07-31 |
| SE446628B (en) | 1986-09-29 |
| ATA60679A (en) | 1981-03-15 |
| SE7900766L (en) | 1979-07-31 |
| DD141305A5 (en) | 1980-04-23 |
| ES477283A1 (en) | 1979-10-16 |
| DE2900060A1 (en) | 1979-08-09 |
| IL56176A0 (en) | 1979-03-12 |
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