CA1128070A - Process for preparing n-alkylethylene diamine - Google Patents
Process for preparing n-alkylethylene diamineInfo
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- CA1128070A CA1128070A CA332,700A CA332700A CA1128070A CA 1128070 A CA1128070 A CA 1128070A CA 332700 A CA332700 A CA 332700A CA 1128070 A CA1128070 A CA 1128070A
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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
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Abstract
27,864 PROCESS FOR PREPARING N-ALKYLETHYLENEDIAMINES
ABSTRACT OF THE DISCLOSURE
This disclosure describes a novel process for pre-paring N-alkylethylenediamines wherein the alkyl is from C3 to about C6 which are useful as intermediates for purifying penicillins. N-alkylethylenediamines are also useful for preparing penicillins and cephalosporins.
More particularly, the invention relates to a pro-cess for the efficient reaction of an alkyl halide wherein the alkyl is from C3 to about C6 and ethylenediamine and the recovery of anhydrous, ethylenediamine-free N-alkylethylene-diamines therefrom.
ABSTRACT OF THE DISCLOSURE
This disclosure describes a novel process for pre-paring N-alkylethylenediamines wherein the alkyl is from C3 to about C6 which are useful as intermediates for purifying penicillins. N-alkylethylenediamines are also useful for preparing penicillins and cephalosporins.
More particularly, the invention relates to a pro-cess for the efficient reaction of an alkyl halide wherein the alkyl is from C3 to about C6 and ethylenediamine and the recovery of anhydrous, ethylenediamine-free N-alkylethylene-diamines therefrom.
Description
Z~3~70 The present invention provides a process for preparing N-alkylethyl-enediamines wherein the alkyl is from C3 to about C6. An alkyl halide wherein the alkyl is from C3 to about C6 is reacted with ethylenediamine (EDA) at a temperature of from about -10C. to about 120C. and at a mole ratio of EDA to said alkyl halide of about 1-20:1, in the presence of about 0-50% by weight of water, to form a reaction mixture containing N-alkylethylenediamine. The res-ulting reaction mixture is then neutralized by contact with an aqueous solution containing about 1 to 2 mol~cular equivalents of an inorganic alkalizing agent based on the alkyl halide to form a mixture consisting of an inorganic halide, an aqueous phase, and an organic phase, from which the organic phase is separa-ted. The organic layer is diluted with about 0.02-100% by weight of a suitable hydrocarbon solvent selected from the group consisting of n-heptane, isooctane, cyclohexane, n-hexane, me~hylcyclohexane and _-pentane, and the resulting mix-ture 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 the N-alkylethyl-enediamine in a purity greater than about 99%.
Preferably, the reaction between the alkyl halide and the EDA is carried out at about 25-50C in the presence of about 0-30% by weight of water and at a mole ratio of EDA to alkyl halide of about 2-5:1. The resulting reac-tion mixture is then contacted with an aqueous caustic soda and the organic layer is dilut0d with about 0.02-20% by weight of the hydrocarbon solvent before carrying out the distillation.
The process of the subject invention can be modified by the addi-tional steps of~ recovering and recycling aqueous EDA from the azeotrope, ~2) recovering and recycling the hydrocarbon solvent, and ~3) contacting the separated, alkalized aqueous layer with about 10-100% by weight of said hydro-`. ~3 ' ~
. :
~2~3~7~
carbon solvent based on the weight of said organic layer, separating the extrac-ted aqueous layer and diluting the organic layer with the hydrocarbon extract before proceeding with the azeotropic fractional distillation.
The present invention also provides processes for the removal of water and/or EDA from the N-alkylethylenediamine by adding a suitable hydrocar-bon solvent thereto, azeotropically fractionally distilling the water andtor EDA therefrom, and fractionally distilling to remove residual hydrocarbon sol-vent and recover anhydrous and/or EDA-free, N-alkylethylenediamine. The advantages of the process of the present invention over previously available processes are that (1) the final product has 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 N-alkylethylenediamine of about 99% purity wherein the alkyl is from C3 to C6 comprising (a) reacting an alkyl halide and EDA at a mole ratio of EDA to said alkyl halide of about 1-20:1 and a tempera-ture of about -10C to about 120C under anhydrous conditions to obtain an alkylation reaction mixture; (b) adding thereto about 0.02-100% by weight, based on the weight of said alkylation reaction mixture of a suitable hydro-carbon solvent selected from the group consisting of n-heptanc, isooctane, cyclohexane, n-hexane, methylcyclohexane and _-pentane; (c) azeotropically fractionally distilling the mixture of EDA and said hydrocarbon solvent to essentially remove EDA from the mixture; (d) neutralizing the resulting reac-tion mixture by contacting it with at least 0.9 molecular equivalent of a suitable alkalizing agent ~,!,.,_ ~ J
~L28~70 per mole of said alkyl halide to form a slurry of an alkali halide precipitate; (e) separating said alkali halide from said slurry and recovering the resulting mother liquor there-from; (f) washing said separated alkali halide with said hydro-5 carbon solvent; (g) azeotropically fractionally distilling acombination of said mother liquor from step (e) plus recov-ered hydrocarbon wash liquor from step (f) to remove essen-tially all water and residual EDA from the resulting mixture;
and (h) fractionally distilling the resulting reaction mix-10 ture to remove residual hydrocarbon solvent and recover saidN-alkylethylenediamine.
EDA, either as an anhydrous liquid or containing water, and an alkyl halide, preferably an alkyl chloride, are admixed in a suitable reactor vessel while agitating and 15 maintaining the reaction mixture at from about -10C to about 120C. (pref~rably at about 25-50C), over a period of about 5-15 hours (preferably about 7-9 hours), to provide a mole ratio of EDA to alkyl halide of about 1-20:1 (preferably about
Preferably, the reaction between the alkyl halide and the EDA is carried out at about 25-50C in the presence of about 0-30% by weight of water and at a mole ratio of EDA to alkyl halide of about 2-5:1. The resulting reac-tion mixture is then contacted with an aqueous caustic soda and the organic layer is dilut0d with about 0.02-20% by weight of the hydrocarbon solvent before carrying out the distillation.
The process of the subject invention can be modified by the addi-tional steps of~ recovering and recycling aqueous EDA from the azeotrope, ~2) recovering and recycling the hydrocarbon solvent, and ~3) contacting the separated, alkalized aqueous layer with about 10-100% by weight of said hydro-`. ~3 ' ~
. :
~2~3~7~
carbon solvent based on the weight of said organic layer, separating the extrac-ted aqueous layer and diluting the organic layer with the hydrocarbon extract before proceeding with the azeotropic fractional distillation.
The present invention also provides processes for the removal of water and/or EDA from the N-alkylethylenediamine by adding a suitable hydrocar-bon solvent thereto, azeotropically fractionally distilling the water andtor EDA therefrom, and fractionally distilling to remove residual hydrocarbon sol-vent and recover anhydrous and/or EDA-free, N-alkylethylenediamine. The advantages of the process of the present invention over previously available processes are that (1) the final product has 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 N-alkylethylenediamine of about 99% purity wherein the alkyl is from C3 to C6 comprising (a) reacting an alkyl halide and EDA at a mole ratio of EDA to said alkyl halide of about 1-20:1 and a tempera-ture of about -10C to about 120C under anhydrous conditions to obtain an alkylation reaction mixture; (b) adding thereto about 0.02-100% by weight, based on the weight of said alkylation reaction mixture of a suitable hydro-carbon solvent selected from the group consisting of n-heptanc, isooctane, cyclohexane, n-hexane, methylcyclohexane and _-pentane; (c) azeotropically fractionally distilling the mixture of EDA and said hydrocarbon solvent to essentially remove EDA from the mixture; (d) neutralizing the resulting reac-tion mixture by contacting it with at least 0.9 molecular equivalent of a suitable alkalizing agent ~,!,.,_ ~ J
~L28~70 per mole of said alkyl halide to form a slurry of an alkali halide precipitate; (e) separating said alkali halide from said slurry and recovering the resulting mother liquor there-from; (f) washing said separated alkali halide with said hydro-5 carbon solvent; (g) azeotropically fractionally distilling acombination of said mother liquor from step (e) plus recov-ered hydrocarbon wash liquor from step (f) to remove essen-tially all water and residual EDA from the resulting mixture;
and (h) fractionally distilling the resulting reaction mix-10 ture to remove residual hydrocarbon solvent and recover saidN-alkylethylenediamine.
EDA, either as an anhydrous liquid or containing water, and an alkyl halide, preferably an alkyl chloride, are admixed in a suitable reactor vessel while agitating and 15 maintaining the reaction mixture at from about -10C to about 120C. (pref~rably at about 25-50C), over a period of about 5-15 hours (preferably about 7-9 hours), to provide a mole ratio of EDA to alkyl halide of about 1-20:1 (preferably about
2-5:1) and form a reaction mixture containing about 0-50% by 20 weight of water (preferably about 0-30%). Suitable alkyl halides include propyl chloride, isopropyl chloride, butyl chloride, pentyl chloride, l-hexyl chloride, and 3-hexyl chloride. The total residence time in the reactor vessel de-pends on the temperature employed, with shorter residence times 25 employed with higher tempera~ures.
The reaction mixture is then vigorously contacted with an aqueous solution of an alkalizing agent to form a mixture, consisting of an organic layer, an aqueous layer, and an alkaline halide. Sufficient alkalizing agent is em-30 ployed so that the pH of the aqueous layer does not go belowabout 7, preferably not below 8 and an aqueous layer is form-ed. Suitable alkalizing agents include sodium and potassium hydroxide, either singly or in mixtures. The preferred al-~28~70 kalizing a~ent is about 50~ a~ueous sodium hydroxide.
The organic layer is separated from the alkaline hal-ide and the aqueous layer by making a phase separation, or by first separating the alkaline halide by filtration or centrifu-gation, and then making a phase separation. The organic layercontains the N-alkylethylenediamine, unreacted EDA, and higher alkylation products such as N,N'-dialkylethylenediamine, N,N--dialkylethylenediamine, N,N,N'-trialkylethylenediamine, and N,N,N',N'-tetraalkylethylenediamine. The organic layer is then diluted with about 0.02-100~ by weight, preferably about 0.02--20~ by weight, of a suitable hydrocarbon solvent, based on the weight of said organic layer.
Preferably, the separated aqueous layer is extracted with about 10-100% by weight, preferably about 10-20% by weight, of said suitable hydrocarbon solvent, based on the weight of said organic layer and the two-phase mlxture is allowed to set-tle. The extracted aqueous layer is then separated and the hydrocarbon solvent extract is used to dilute the above- men-tioned organic layer.
As employed herein, the term "suitable hydrocarbon solvent" is defined as a hydrocarbon solvent which forms an azeo-trope with water and/or EDA below the boiling point of the pro-duct N-alkylethylenediamine from which condensed azeotrope water and/or EDA may be separated from the hydrocarbon without in-clusion of substantial amount of the N-alkylethylenediamine.
Suitable hydrocarbon solvents include n-heptane, isooctane, cyclohexane, n-hexane, methylcyclohexane, n-pentane, and the li~e, although the preferred hydrocarbon solvent is n-heptane.
The diluted organic layer is then heated to boiling through a distillation column to azeotropically fractionally distill off any residual EDA and water. After allowing the distillate to settle, the lower EDA-water layer may be s~a-rated and recycled to the alkylation vessel, and the upper hydrocarbon layer may be recycled to the distillation column until anhydrous EDA-free N-alkylethylenediamine is obtained, :
-: .
llZ~070 or transferred to a vessel for extraction of the original aqu-eous layer.
The residual EDA-free reaction mixture, containing N-alkylethylenediamine, higher alkylated ethylenediamines, and the hydrocarbon solvent is now fractionally distilled, using a fractionation column containing sufficient theoretical plates, to separate said hydrocarbon solvent from the N-alkylethylene-diamine. For example, using a column containing 15 theoretical plates and n-heptane as the solvent, the n-heptane distills off as a forerun boiling at about 98-100C. The forerun of hydrocarbon solvent so obtained may be recycled to other sta-ges of the process, such as dilution of the organic layer, azeotroping EDA and water from the reaction mixture, or ex-tracting the aqueous layer, as described above.
After removal of the forerun of hydrocarbon solvent, the distillation is continued to obtain the N-alkylethylene-diamine (purity greater than 99%) in a yield of greater than 60% based on the alkyl halide charged. The procedure employed herein may also be used to remove water and/or EDA from the W-alkylethylenediamine by adding a suitable amount of said hydrocarbon solvent thereto, azeotropically fractionally dls-tilling the water or EDA, or both, therefrom and fractionally distilling the residue to remove excess hydrocarbon solvent and obtain anhydrous, ~DA-free N-alkylethylenediamine. It is to be understood that the aforedescribed process may also be carried out continuously using appropriate vessels, such as continuous flow reactors, splitter vessels, distillation col-umns, and the like.
In an alternative process ethylenediamine as an an-hydrous liquid, is reacted with an alkyl halide as shown below H
RX + H2N-CH2CH2-NH2 > R-NCH2CH2NH2 + HX
wherein X is a halo atom, such as chloro, bromo, or iodo, preferably chloro. The reaction is carried out while agitating the reaction mixture in a suitable reactor vessel ~28~70 at about -10C to about 120C, preferably at about 25-75C, over a period of about 1-24 hours, preferably about 2-6 hours. The mole ratio of EDA to the alkyl halide employed is about 1-20 to 1, preferably about 2-5 to l. The total residence time in the reactor vessel will depend on the temperature employed, with shorter residence times employed with higher temperatures.
Upon completion of the reaction, the reaction mixture is diluted with about 0.02-100% by weight, preferably about 0.5-1.0% by weight, of a suitable hydrocarbon solvent, based on the weight of the reaction mixture. As employed herein the term "suitable hydrocarbon solvent" has the same meaning as previ-ously defined. The diluted reaction mixture is then heated to boiling througha distillation column to azeotropically fractionally distill off any residual EDA. Optionally, the EDA distillate may be recovered and recycled.
Suitable hydrocarbon solvents include _-heptane, isooctane, cyclohex-ane, n-hexane, methylcyclohexane, n-pentane, and the like, although the pre-ferred hydrocarbon solvent is n-heptane.
The reaction mixture is then neutralized by contacting it with at least 0.9 molecular equivalent of a suitable alkalizing agent per mole of alkyl halide used. As employed herein the term "suitable alkalizing agent" is defined as sodium or potassium hydroxide, either singly or in mixtures. The preferred alkalizing agent is 50% aqueous sodium hydroxide.
The resulting alkali halide precipitate is separated from the result-ing slurry by conventional means, such as filtration or centrifugation, and washed Wit]l the hydrocarbon solvent described previously, preferably with _-heptane~
The hydrocarbon solvent wash liquors are collected and combined with the mother liquor obtained by the separation of the alkali halide precipitate from the slurry formed by the addition of an alkalizing agent to the reaction mixture. The combined liquors are azeotropically fractionally ~128~0 distilled at atmospheric pressure through a packed column, preferably with recycle of heptane distillate to the column, until the residual material is essentially free of EDA and water.
The resulting essentially EDA-free reaction mixture, containing the product N-alkylethylenediamine, higher alkyl-ated ethylenediamines, and the hydrocarbon solvent is now fractionally distilled, using a fractionation column contain-ing sufficient theoretical plates, to separate said hydrocar-bon solvent from the product N-alkylethylenediamine. For ex-ample, using a column containing lS theoretical plates, n--he~iane distills off as a forerun boiling at about 98-100C.
The forerun of hydrocarbon solvent so obtained may be recyc-led to other stages of the process, such as dilution of the lS reaction mixture, or azeotroping EDA or water from the reac-tion mixture.
After removal of t.he forerun of hydrocarbon solvent the reaction mixture is preferably clarified to remove any insolubles and distillation of the clarified solution is con-tinued to obtain the N-alkylethylenediamine in a purity great-er than 99~ and a yield of greater than 60% of theoretical based on the alkyl halide charged.
It is to be understood that the aforedescribed pro-cess may also be carried out continuously using appropriate vessels, such as continuous Elow reactors, separation vessels, distillation columns, and the like.
I The following examples are provided to illustrate j the invention. Except as otherwise noted, all parts are by weight and all ranges are inclusive of both numbers. The purity of the product i5 expressed as area percent, as deter-mined 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 anhydrous EDA (1420 grams; 23.63 moles) at 30-40C over a .
1:~28~7~
- ~8 -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 mixture is stirred for 30 minutes, allowed to settle, and the aqueous salt slurry is separated and extracted twice with 150 ml of _-he~tane. The heptane extracts are added to the organic phase and the combined solution is heated to azeotropically distill water and EDA therefrom at 88-97C., using a frac-tionation column and a splitter device to return distilled heptane to the distillation column and to separate the denser aqueous EDA phase. In this manner an aqueous EDA phase is se~arated consisting of 394 grams of water and 896 grams of EDA (14.91 moles). The EDA-free residue is fractionally dis-tilled to obtain a heptane forerun (b.p. 98-102C.) contain-ing 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 use of recovered aqueous EDA
Ethyl chloride (545 grams; 8.45 moles) is added at 30-40C. over a period of S hours to a mixture of 1245 grams of aqueous EDA recovered fron; Example 1 (containing 14.39 moles of EDA) and anhydrous EDA (555 grams; 9.23 moles). The reaction mixture is stirred for 2 hours after the addition is completed and 50% caustic soda (902 ml; 16.9 moles) is added thereto. The resulting mixture is processed as described in Example 1 utilizing recovered n-heptane from Example 1 to ex-tract the separated aqueous salt slurry. Fractional distil-lation 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~ purity by VPC.
The yield is 65% of theoretical based on ethyl chloride.
Example 3 ; This example illustrates the separation of EDA from N-Ethyl--ethylenediamine by azeotropic distillation :; :
, 1~28(~
A mixture of EDA (500 grams) and NEED (500 grams) is diluted with 200 ml. of n-heptane and heated to azeotrop-ically fractionally distill (b.p. 87-90C) EDA therefrom, using a distillation column and a device which returns the recovered heptane to the distillation apparatus and allows for tile recovery of the denser EDA phase. The EDA thus re-covered contains less than 1% NEED by VPC. The EDA-free re-sidue is then fractionally distilled to recover a heptane forerun and pure NEED (b.p. 130-131C).
In the manner described above, substituting cyclo-hexane, n-hexane, or isooctane for the n-heptane, similar re-sults are obtained.
Example 4 This example illustrates the separation of water from N-Eth-ylethYlenediamine 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.
88-98C) therefrom using a distillation column and a split-ter apparatus which returns the recovered heptane to thedistillation apparatus and allows for the removal of the den~
ser water phase. After removal of the water is complete, the residue is fractionally distilled to recover a heptane fore-run and NEED (b.p. 130-131C) containing less than 0.2%
water by VPC.
In the manner descri~ed above, substituting cyclo-hexane, n-hexane, or isooctane for the n-heptane, similar re-sults are obtained.
Examples 5 to 10 illustrate the recovery of N-ethylethylene-diamine wherein the EDA is removed before neutralization Example 5 Ethyl chloride (62.4 grams; 0.967 mole) is added to8tirred ethylenediamine (146.3 grams; 2.43 moles) over a per-iod 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 mix-ture is azeotropically distilled using a fractionation column and a Dean~Stark device to collect the two-phase liquid dis-tillate consisting of a lower layer of ethylenediamine (85.09 grams) and an upper layer of heptane which is recycled back to the fractionation column until all of the ethylenediamine is removed therefrom.
The remaining material is cooled to 80C, neutra-lized with 50~ aqueous sodium hydroxide (77.36 grams; 0.967 mole) and the resulting precipitate of sodium chloride is separated by filtration to obtain a filter cake and a two--phase liquid filtrate. The filter cake is then washed with heptane (50 mls) and the washing is added to the original two-phase filtrate.
The resulting two-phase liquid is then azeotropic-ally 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-ethylethylenediar,line (54.5 grams; b.p. 130-131C;
64% of theoretical) in a purity of 99%.
Example 6 The procedure of Example 5 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 filter cake is then washed with heptane (16 grams) and the washing is combined with the filtrate. The combined filtrate plus washing is then fractionally distilled to remove heptane and recover N-ethylethylenediamine (53.7 grams; b.p. 130-131C; 63% of theoretical) in 99% purity.
Example 7 To a glass-lined reactor is charged 848 parts of ethylenediamine (98%) followed by 331 parts of liquid ethyl chloride, charged through a dip leg at a rate to maintain the ~28~
reaction mixture at 45-55~C. 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 recycle of the heptane distillate to the top of the column. A total of 492 parts of ethylenediamine is recovered from the distillate for recycle. The reaction mixture is neutralized with 402 parts of 50~ caustic soda, cooled to room temperature, and centrifuged 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 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 removed the heptane is fractionally distilled off through the packed column to ob-tain a residue containing 273 parts of N-ethylethylenediamine.
This residue is reserved for subsequent combination with the residues of ExampleS 8-10.
Example 8 To a glass-lined reactor is charged 492 parts of : recovered 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 recovered heptane from Example 7 are added there-to. The excess ethylenediamine is azeotropically distilled off through a packed column with recycle of the heptane dis-¦ tillate to top of the column. A total of 501 parts of ethyl-¦ enediamine is recovered from the distillate for recycle. The 1 30 reaction mixture is neutralized with 407 parts of 50% caustic ~oda, cooled to room temperature, and centrifuged to remove the sodium chloride by-product. The salt calce is washed with 78 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined vessel. Water is azeotropical-ly distilled off from the combined liquors through a packed ..
., . . ~ ,~
112~3~7(~
column with recycle of the distilled heptane to the top of the column. After all of the water is removed the heptane is fractionally distilled off through the packed column to obtain a residue containin~ 288 parts of N-ethylethylenediamine.
This residue is reserved for subsequent combination with the resid-~es of Examples 7, 9 and 10.
Example 9 To a glass-lined reactor is charged 501 parts of re-covered ethylenediamine from Example 8 and 396 parts of fresh ethylenediamine (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 for 2 hours and 28 parts of recovered heptane from Example 8 are added thereto. The excess ethylenediamine is azeotropically distilled off through a packed column with recycle of the heptane distillate to the top of the column. A total of 504 parts of ethylenediamine is recovered from the distillate for recycle. The reaction mixture is neutralized with 409 parts of 50% caustic soda, cooled to room temperature, and centrifuged to remove the sodium chloride by-product. The salt cake is washed with 82 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined vessel. Water is azeotropical-ly 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 removed the heptane is fractionally distilled off through the packed column to obtain a residue containing 310 parts of N-ethylethylenediamine. This residue is reserved for subsequent combination with the resi-dues of Examples 7, 8 and 10.
Example 10 To a glass-lined reactor is charged 504 parts of re-covered ethylenediamine from Example 9 and 388 parts of fresh ethylenediamine (98%). To this mixture is charged 331 parts of ethyl chloride at a rate to maintain the reaction mixture 35 at 5S-65C. The mixture is stirred for 2 hours and 30 parts 112~3~70 of recovered heptane from Example 9 are added thereto. The ex-cess ethylenediamine is a~eotropically distilled off through a packed column with recycle of the heptane distillate to the top o~ the column. A total of 523 parts of ethylenediamine 5 is recovered from the distillate for recycle. The reaction mixture is neutralized with 409 parts of 50~ caustic soda, cooled to room temperature, and centrifuged to remove the sod-ium chloride by-product. The salt cake is washed with 91 parts of heptane and the wash liquor is combined with the mot-10 her liquor in a glass-lined vessel. Water is azeotropically distilled off from the combined liquors through a packed col-umn Witl recycle of the distilled heptane to the top of the column. After all of the water is removed the heptane is fractionally distilled off through the packed column to obtain 15 a residue containing 317 parts of N-ethylethylenediamine 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-eth-ylethylenediamine, b.p. 129-131C. The yield is 61.9% of 20 theoretical based on ethyl chloride.
Examples ll_to 13 illustrate the use of n-proPYl halide, iso-propyl halide and n-butyl halide, respectively, in the invention Exam~le 11 n-Propyl chloride (327.1 grams; 4.16 moles) is added 25 to anhydrous EDA (988.9 gram3; 16.48 moles) at 20-24C over a period of one hour. The reaction mixture is stirred for 4 hours after the addition is completed and 50~ caustic soda ~392 ml; 7.35 moles) and water (206 mls) are added thereto.
The resulting mixture is allowed to settle, and the aqueous 30 salt slurry is separated and extracted twice with 280 ml of n-heptane. The heptane extracts are added to the organic phase and the combined mixture is heated to azeotropically distill water and EDA therefrom at 88-97C, using a splitter device to return distilled heptane to the distillation vessel and to 35 separate the denser aqueous EDA phase. The EDA-free residue `` l~Z8~17(~ .
is then fractionally distilled to obtain a heptane forerun (b.p. 97-100C), and a main fraction of 341.3 grams of N-n--propylethylenediamine (b.p. 75-77C at 60 mm) of greater than 99% purity by VPC. The yield is 79.5~ of theoretical based on n-propyl chloride.
Calculated for CsH14N2 : C, 58.77; H, 13.81; N, 27.42 Found : C, 59.08; H, 13.87; N, 27.60 Example 12 Isopropyl chloride (327 grams; 4.16 moles) is added to anhydrous EDA (988.9 grams; 16.48 moles) at 70C. After the addition is completed, the reaction mixture is slowly heat-ed to 100C, cooled to 25C, and mixed with 50% caustic soda ~391 mls; 7.35 moles) and water (206 mls). The resulting mix-ture is allowed to settle, and the aqueous salt slurry is lS separated and extracted twice with 200 mls of n-heptane. The heptane extracts are added to the organic phase and the com-bined mixture is heated to azeotropically distill water and EDA therefrom at 88-97C, using a splitter device to return distilled heptane to the distillation vessel and to separate the denser aqueous EDA phase. The EDA-free residue is then fractionally distilled to obtain a heptane forerun (b.p. 97-100C), and a main fraction of 305 grams of N-isopropylethyl-enediamine (b.p. 136-137C) of greater than 99~ purity by VPC. The yield is 71.1% of theoretical based on isopropyl chloride.
Calculated for C5H14~2 : C, 58.77; H, 13.81; N, 27.42 Found : C, 59.16; H, 13.89; N, 27.28 Example 13 n-Butyl chloride (385.4 grams; 4.16 moles) is added to anhydrous EDA ~979.0 grams; 16.29 moles) at 20-24C over a period of one hour. The reaction mixture is stirred at 22-27C for 4 hours after the addition is completed and 50% cau-stic soda (935 ml; 7.35 moles) and water (207 mls) are added thereto. The resulting mixture is allowed to settle, and the aqueous salt slurry is separated and extracted twice with 200 '~ ~
mls of n-heptane. The heptane extracts are added ta the organ-ic phase and the combined mixture is heated to azeotropically distill water and EDA therefrom at 88-97C, using a splitter device to return distilled heptane to the distillation vessel and to separate the denser aqueous EDA phase. The EDA-free residue is then fractionally distilled to obtain a heptane fore-run (b.p. 96-100C) and a main fraction of 348 grams of N-n--butylethylenediamine (b.p. 74-77C at 20-30 mm) of greater than 99% purity by VPC. The yield is 71.3% of theoretical based on n-butyl chloride.
Calculated for C6H16N2 : C, 62.01; H, 13.88; N, 24.11 Found : C, 61.51; H, 13.92; N, 24.13 , I
.j ~
~.
The reaction mixture is then vigorously contacted with an aqueous solution of an alkalizing agent to form a mixture, consisting of an organic layer, an aqueous layer, and an alkaline halide. Sufficient alkalizing agent is em-30 ployed so that the pH of the aqueous layer does not go belowabout 7, preferably not below 8 and an aqueous layer is form-ed. Suitable alkalizing agents include sodium and potassium hydroxide, either singly or in mixtures. The preferred al-~28~70 kalizing a~ent is about 50~ a~ueous sodium hydroxide.
The organic layer is separated from the alkaline hal-ide and the aqueous layer by making a phase separation, or by first separating the alkaline halide by filtration or centrifu-gation, and then making a phase separation. The organic layercontains the N-alkylethylenediamine, unreacted EDA, and higher alkylation products such as N,N'-dialkylethylenediamine, N,N--dialkylethylenediamine, N,N,N'-trialkylethylenediamine, and N,N,N',N'-tetraalkylethylenediamine. The organic layer is then diluted with about 0.02-100~ by weight, preferably about 0.02--20~ by weight, of a suitable hydrocarbon solvent, based on the weight of said organic layer.
Preferably, the separated aqueous layer is extracted with about 10-100% by weight, preferably about 10-20% by weight, of said suitable hydrocarbon solvent, based on the weight of said organic layer and the two-phase mlxture is allowed to set-tle. The extracted aqueous layer is then separated and the hydrocarbon solvent extract is used to dilute the above- men-tioned organic layer.
As employed herein, the term "suitable hydrocarbon solvent" is defined as a hydrocarbon solvent which forms an azeo-trope with water and/or EDA below the boiling point of the pro-duct N-alkylethylenediamine from which condensed azeotrope water and/or EDA may be separated from the hydrocarbon without in-clusion of substantial amount of the N-alkylethylenediamine.
Suitable hydrocarbon solvents include n-heptane, isooctane, cyclohexane, n-hexane, methylcyclohexane, n-pentane, and the li~e, although the preferred hydrocarbon solvent is n-heptane.
The diluted organic layer is then heated to boiling through a distillation column to azeotropically fractionally distill off any residual EDA and water. After allowing the distillate to settle, the lower EDA-water layer may be s~a-rated and recycled to the alkylation vessel, and the upper hydrocarbon layer may be recycled to the distillation column until anhydrous EDA-free N-alkylethylenediamine is obtained, :
-: .
llZ~070 or transferred to a vessel for extraction of the original aqu-eous layer.
The residual EDA-free reaction mixture, containing N-alkylethylenediamine, higher alkylated ethylenediamines, and the hydrocarbon solvent is now fractionally distilled, using a fractionation column containing sufficient theoretical plates, to separate said hydrocarbon solvent from the N-alkylethylene-diamine. For example, using a column containing 15 theoretical plates and n-heptane as the solvent, the n-heptane distills off as a forerun boiling at about 98-100C. The forerun of hydrocarbon solvent so obtained may be recycled to other sta-ges of the process, such as dilution of the organic layer, azeotroping EDA and water from the reaction mixture, or ex-tracting the aqueous layer, as described above.
After removal of the forerun of hydrocarbon solvent, the distillation is continued to obtain the N-alkylethylene-diamine (purity greater than 99%) in a yield of greater than 60% based on the alkyl halide charged. The procedure employed herein may also be used to remove water and/or EDA from the W-alkylethylenediamine by adding a suitable amount of said hydrocarbon solvent thereto, azeotropically fractionally dls-tilling the water or EDA, or both, therefrom and fractionally distilling the residue to remove excess hydrocarbon solvent and obtain anhydrous, ~DA-free N-alkylethylenediamine. It is to be understood that the aforedescribed process may also be carried out continuously using appropriate vessels, such as continuous flow reactors, splitter vessels, distillation col-umns, and the like.
In an alternative process ethylenediamine as an an-hydrous liquid, is reacted with an alkyl halide as shown below H
RX + H2N-CH2CH2-NH2 > R-NCH2CH2NH2 + HX
wherein X is a halo atom, such as chloro, bromo, or iodo, preferably chloro. The reaction is carried out while agitating the reaction mixture in a suitable reactor vessel ~28~70 at about -10C to about 120C, preferably at about 25-75C, over a period of about 1-24 hours, preferably about 2-6 hours. The mole ratio of EDA to the alkyl halide employed is about 1-20 to 1, preferably about 2-5 to l. The total residence time in the reactor vessel will depend on the temperature employed, with shorter residence times employed with higher temperatures.
Upon completion of the reaction, the reaction mixture is diluted with about 0.02-100% by weight, preferably about 0.5-1.0% by weight, of a suitable hydrocarbon solvent, based on the weight of the reaction mixture. As employed herein the term "suitable hydrocarbon solvent" has the same meaning as previ-ously defined. The diluted reaction mixture is then heated to boiling througha distillation column to azeotropically fractionally distill off any residual EDA. Optionally, the EDA distillate may be recovered and recycled.
Suitable hydrocarbon solvents include _-heptane, isooctane, cyclohex-ane, n-hexane, methylcyclohexane, n-pentane, and the like, although the pre-ferred hydrocarbon solvent is n-heptane.
The reaction mixture is then neutralized by contacting it with at least 0.9 molecular equivalent of a suitable alkalizing agent per mole of alkyl halide used. As employed herein the term "suitable alkalizing agent" is defined as sodium or potassium hydroxide, either singly or in mixtures. The preferred alkalizing agent is 50% aqueous sodium hydroxide.
The resulting alkali halide precipitate is separated from the result-ing slurry by conventional means, such as filtration or centrifugation, and washed Wit]l the hydrocarbon solvent described previously, preferably with _-heptane~
The hydrocarbon solvent wash liquors are collected and combined with the mother liquor obtained by the separation of the alkali halide precipitate from the slurry formed by the addition of an alkalizing agent to the reaction mixture. The combined liquors are azeotropically fractionally ~128~0 distilled at atmospheric pressure through a packed column, preferably with recycle of heptane distillate to the column, until the residual material is essentially free of EDA and water.
The resulting essentially EDA-free reaction mixture, containing the product N-alkylethylenediamine, higher alkyl-ated ethylenediamines, and the hydrocarbon solvent is now fractionally distilled, using a fractionation column contain-ing sufficient theoretical plates, to separate said hydrocar-bon solvent from the product N-alkylethylenediamine. For ex-ample, using a column containing lS theoretical plates, n--he~iane distills off as a forerun boiling at about 98-100C.
The forerun of hydrocarbon solvent so obtained may be recyc-led to other stages of the process, such as dilution of the lS reaction mixture, or azeotroping EDA or water from the reac-tion mixture.
After removal of t.he forerun of hydrocarbon solvent the reaction mixture is preferably clarified to remove any insolubles and distillation of the clarified solution is con-tinued to obtain the N-alkylethylenediamine in a purity great-er than 99~ and a yield of greater than 60% of theoretical based on the alkyl halide charged.
It is to be understood that the aforedescribed pro-cess may also be carried out continuously using appropriate vessels, such as continuous Elow reactors, separation vessels, distillation columns, and the like.
I The following examples are provided to illustrate j the invention. Except as otherwise noted, all parts are by weight and all ranges are inclusive of both numbers. The purity of the product i5 expressed as area percent, as deter-mined 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 anhydrous EDA (1420 grams; 23.63 moles) at 30-40C over a .
1:~28~7~
- ~8 -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 mixture is stirred for 30 minutes, allowed to settle, and the aqueous salt slurry is separated and extracted twice with 150 ml of _-he~tane. The heptane extracts are added to the organic phase and the combined solution is heated to azeotropically distill water and EDA therefrom at 88-97C., using a frac-tionation column and a splitter device to return distilled heptane to the distillation column and to separate the denser aqueous EDA phase. In this manner an aqueous EDA phase is se~arated consisting of 394 grams of water and 896 grams of EDA (14.91 moles). The EDA-free residue is fractionally dis-tilled to obtain a heptane forerun (b.p. 98-102C.) contain-ing 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 use of recovered aqueous EDA
Ethyl chloride (545 grams; 8.45 moles) is added at 30-40C. over a period of S hours to a mixture of 1245 grams of aqueous EDA recovered fron; Example 1 (containing 14.39 moles of EDA) and anhydrous EDA (555 grams; 9.23 moles). The reaction mixture is stirred for 2 hours after the addition is completed and 50% caustic soda (902 ml; 16.9 moles) is added thereto. The resulting mixture is processed as described in Example 1 utilizing recovered n-heptane from Example 1 to ex-tract the separated aqueous salt slurry. Fractional distil-lation 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~ purity by VPC.
The yield is 65% of theoretical based on ethyl chloride.
Example 3 ; This example illustrates the separation of EDA from N-Ethyl--ethylenediamine by azeotropic distillation :; :
, 1~28(~
A mixture of EDA (500 grams) and NEED (500 grams) is diluted with 200 ml. of n-heptane and heated to azeotrop-ically fractionally distill (b.p. 87-90C) EDA therefrom, using a distillation column and a device which returns the recovered heptane to the distillation apparatus and allows for tile recovery of the denser EDA phase. The EDA thus re-covered contains less than 1% NEED by VPC. The EDA-free re-sidue is then fractionally distilled to recover a heptane forerun and pure NEED (b.p. 130-131C).
In the manner described above, substituting cyclo-hexane, n-hexane, or isooctane for the n-heptane, similar re-sults are obtained.
Example 4 This example illustrates the separation of water from N-Eth-ylethYlenediamine 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.
88-98C) therefrom using a distillation column and a split-ter apparatus which returns the recovered heptane to thedistillation apparatus and allows for the removal of the den~
ser water phase. After removal of the water is complete, the residue is fractionally distilled to recover a heptane fore-run and NEED (b.p. 130-131C) containing less than 0.2%
water by VPC.
In the manner descri~ed above, substituting cyclo-hexane, n-hexane, or isooctane for the n-heptane, similar re-sults are obtained.
Examples 5 to 10 illustrate the recovery of N-ethylethylene-diamine wherein the EDA is removed before neutralization Example 5 Ethyl chloride (62.4 grams; 0.967 mole) is added to8tirred ethylenediamine (146.3 grams; 2.43 moles) over a per-iod 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 mix-ture is azeotropically distilled using a fractionation column and a Dean~Stark device to collect the two-phase liquid dis-tillate consisting of a lower layer of ethylenediamine (85.09 grams) and an upper layer of heptane which is recycled back to the fractionation column until all of the ethylenediamine is removed therefrom.
The remaining material is cooled to 80C, neutra-lized with 50~ aqueous sodium hydroxide (77.36 grams; 0.967 mole) and the resulting precipitate of sodium chloride is separated by filtration to obtain a filter cake and a two--phase liquid filtrate. The filter cake is then washed with heptane (50 mls) and the washing is added to the original two-phase filtrate.
The resulting two-phase liquid is then azeotropic-ally 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-ethylethylenediar,line (54.5 grams; b.p. 130-131C;
64% of theoretical) in a purity of 99%.
Example 6 The procedure of Example 5 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 filter cake is then washed with heptane (16 grams) and the washing is combined with the filtrate. The combined filtrate plus washing is then fractionally distilled to remove heptane and recover N-ethylethylenediamine (53.7 grams; b.p. 130-131C; 63% of theoretical) in 99% purity.
Example 7 To a glass-lined reactor is charged 848 parts of ethylenediamine (98%) followed by 331 parts of liquid ethyl chloride, charged through a dip leg at a rate to maintain the ~28~
reaction mixture at 45-55~C. 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 recycle of the heptane distillate to the top of the column. A total of 492 parts of ethylenediamine is recovered from the distillate for recycle. The reaction mixture is neutralized with 402 parts of 50~ caustic soda, cooled to room temperature, and centrifuged 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 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 removed the heptane is fractionally distilled off through the packed column to ob-tain a residue containing 273 parts of N-ethylethylenediamine.
This residue is reserved for subsequent combination with the residues of ExampleS 8-10.
Example 8 To a glass-lined reactor is charged 492 parts of : recovered 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 recovered heptane from Example 7 are added there-to. The excess ethylenediamine is azeotropically distilled off through a packed column with recycle of the heptane dis-¦ tillate to top of the column. A total of 501 parts of ethyl-¦ enediamine is recovered from the distillate for recycle. The 1 30 reaction mixture is neutralized with 407 parts of 50% caustic ~oda, cooled to room temperature, and centrifuged to remove the sodium chloride by-product. The salt calce is washed with 78 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined vessel. Water is azeotropical-ly distilled off from the combined liquors through a packed ..
., . . ~ ,~
112~3~7(~
column with recycle of the distilled heptane to the top of the column. After all of the water is removed the heptane is fractionally distilled off through the packed column to obtain a residue containin~ 288 parts of N-ethylethylenediamine.
This residue is reserved for subsequent combination with the resid-~es of Examples 7, 9 and 10.
Example 9 To a glass-lined reactor is charged 501 parts of re-covered ethylenediamine from Example 8 and 396 parts of fresh ethylenediamine (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 for 2 hours and 28 parts of recovered heptane from Example 8 are added thereto. The excess ethylenediamine is azeotropically distilled off through a packed column with recycle of the heptane distillate to the top of the column. A total of 504 parts of ethylenediamine is recovered from the distillate for recycle. The reaction mixture is neutralized with 409 parts of 50% caustic soda, cooled to room temperature, and centrifuged to remove the sodium chloride by-product. The salt cake is washed with 82 parts of heptane and the wash liquor is combined with the mother liquor in a glass-lined vessel. Water is azeotropical-ly 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 removed the heptane is fractionally distilled off through the packed column to obtain a residue containing 310 parts of N-ethylethylenediamine. This residue is reserved for subsequent combination with the resi-dues of Examples 7, 8 and 10.
Example 10 To a glass-lined reactor is charged 504 parts of re-covered ethylenediamine from Example 9 and 388 parts of fresh ethylenediamine (98%). To this mixture is charged 331 parts of ethyl chloride at a rate to maintain the reaction mixture 35 at 5S-65C. The mixture is stirred for 2 hours and 30 parts 112~3~70 of recovered heptane from Example 9 are added thereto. The ex-cess ethylenediamine is a~eotropically distilled off through a packed column with recycle of the heptane distillate to the top o~ the column. A total of 523 parts of ethylenediamine 5 is recovered from the distillate for recycle. The reaction mixture is neutralized with 409 parts of 50~ caustic soda, cooled to room temperature, and centrifuged to remove the sod-ium chloride by-product. The salt cake is washed with 91 parts of heptane and the wash liquor is combined with the mot-10 her liquor in a glass-lined vessel. Water is azeotropically distilled off from the combined liquors through a packed col-umn Witl recycle of the distilled heptane to the top of the column. After all of the water is removed the heptane is fractionally distilled off through the packed column to obtain 15 a residue containing 317 parts of N-ethylethylenediamine 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-eth-ylethylenediamine, b.p. 129-131C. The yield is 61.9% of 20 theoretical based on ethyl chloride.
Examples ll_to 13 illustrate the use of n-proPYl halide, iso-propyl halide and n-butyl halide, respectively, in the invention Exam~le 11 n-Propyl chloride (327.1 grams; 4.16 moles) is added 25 to anhydrous EDA (988.9 gram3; 16.48 moles) at 20-24C over a period of one hour. The reaction mixture is stirred for 4 hours after the addition is completed and 50~ caustic soda ~392 ml; 7.35 moles) and water (206 mls) are added thereto.
The resulting mixture is allowed to settle, and the aqueous 30 salt slurry is separated and extracted twice with 280 ml of n-heptane. The heptane extracts are added to the organic phase and the combined mixture is heated to azeotropically distill water and EDA therefrom at 88-97C, using a splitter device to return distilled heptane to the distillation vessel and to 35 separate the denser aqueous EDA phase. The EDA-free residue `` l~Z8~17(~ .
is then fractionally distilled to obtain a heptane forerun (b.p. 97-100C), and a main fraction of 341.3 grams of N-n--propylethylenediamine (b.p. 75-77C at 60 mm) of greater than 99% purity by VPC. The yield is 79.5~ of theoretical based on n-propyl chloride.
Calculated for CsH14N2 : C, 58.77; H, 13.81; N, 27.42 Found : C, 59.08; H, 13.87; N, 27.60 Example 12 Isopropyl chloride (327 grams; 4.16 moles) is added to anhydrous EDA (988.9 grams; 16.48 moles) at 70C. After the addition is completed, the reaction mixture is slowly heat-ed to 100C, cooled to 25C, and mixed with 50% caustic soda ~391 mls; 7.35 moles) and water (206 mls). The resulting mix-ture is allowed to settle, and the aqueous salt slurry is lS separated and extracted twice with 200 mls of n-heptane. The heptane extracts are added to the organic phase and the com-bined mixture is heated to azeotropically distill water and EDA therefrom at 88-97C, using a splitter device to return distilled heptane to the distillation vessel and to separate the denser aqueous EDA phase. The EDA-free residue is then fractionally distilled to obtain a heptane forerun (b.p. 97-100C), and a main fraction of 305 grams of N-isopropylethyl-enediamine (b.p. 136-137C) of greater than 99~ purity by VPC. The yield is 71.1% of theoretical based on isopropyl chloride.
Calculated for C5H14~2 : C, 58.77; H, 13.81; N, 27.42 Found : C, 59.16; H, 13.89; N, 27.28 Example 13 n-Butyl chloride (385.4 grams; 4.16 moles) is added to anhydrous EDA ~979.0 grams; 16.29 moles) at 20-24C over a period of one hour. The reaction mixture is stirred at 22-27C for 4 hours after the addition is completed and 50% cau-stic soda (935 ml; 7.35 moles) and water (207 mls) are added thereto. The resulting mixture is allowed to settle, and the aqueous salt slurry is separated and extracted twice with 200 '~ ~
mls of n-heptane. The heptane extracts are added ta the organ-ic phase and the combined mixture is heated to azeotropically distill water and EDA therefrom at 88-97C, using a splitter device to return distilled heptane to the distillation vessel and to separate the denser aqueous EDA phase. The EDA-free residue is then fractionally distilled to obtain a heptane fore-run (b.p. 96-100C) and a main fraction of 348 grams of N-n--butylethylenediamine (b.p. 74-77C at 20-30 mm) of greater than 99% purity by VPC. The yield is 71.3% of theoretical based on n-butyl chloride.
Calculated for C6H16N2 : C, 62.01; H, 13.88; N, 24.11 Found : C, 61.51; H, 13.92; N, 24.13 , I
.j ~
~.
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing an N-alkylethylenediamine wherein the alkyl is from C3 to about C6 comprising reacting ethylenediamine (EDA) and an alkyl halide at a mole ratio of EDA to said alkyl 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 alkyl halide; separating the inorganic halide and the aqueous layer from the neutralized organic layer and adding to said organic layer about 0.02-100% by weight, based on the weight of said organic layer, of a suitable hydrocarbon solvent selected from the group consisting of n-heptane, isooctane, cyclohexane, n-hexane, methylcyclohexane and n-pentane, azeotropically fractionally distilling all the EDA and water from the resulting mixture; and fractionally distilling the resulting reaction mixture to remove residual hydrocarbon solvent and recover said N-alkylethylenediamine in a purity greater than about 99%.
neutralizing said reaction mixture by contacting with an aqueous solution containing about 1-2 molecular equivalents of an inorganic alkalizing agent based on the alkyl halide; separating the inorganic halide and the aqueous layer from the neutralized organic layer and adding to said organic layer about 0.02-100% by weight, based on the weight of said organic layer, of a suitable hydrocarbon solvent selected from the group consisting of n-heptane, isooctane, cyclohexane, n-hexane, methylcyclohexane and n-pentane, azeotropically fractionally distilling all the EDA and water from the resulting mixture; and fractionally distilling the resulting reaction mixture to remove residual hydrocarbon solvent and recover said N-alkylethylenediamine in a purity greater than about 99%.
2. A process according to Claim 1 wherein said EDA and alkyl halide are reacted at a mole ratio of EDA to said alkyl halide of about 2-5:1 and a temperature of about 25°-50°C in the presence of about 0-30% by weight of water to obtain said alkylation reaction mixture; said reaction mixture is neutralized by contacting with aqueous caustic soda; and about 0.02-20% by weight of said hydrocarbon is added to said organic layer.
3. A process according to Claim 1 wherein said hydrocarbon is n-heptane.
4. A process according to Claim 2 wherein said hydrocarbon is n-heptane.
5. A process for preparing an N-alkylethylenediamine according to Claim 1 including the additional steps of (a) recovering aqueous EDA from the azeotrope and recycling to react with said alkyl halide; and (b) recovering the hydrocarbon solvent from the forerun of the distillation of said N-alkylethylenediamine and recycling to the distillation mixture.
6. A process according to Claim 1 with the additional 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 before proceeding with said azeotropic fractional distillation.
7. A process according to Claim 5 with the additional 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.
8. A process according to Claim 3, 4 or 5 wherein said alkyl halide is an alkyl chloride.
9. A process for preparing N-alkylethylenediamine wherein the alkyl is from C3 to C6 of about 99% purity comprising (a) reacting an alkyl halide and ethylenediamine (EDA) at a mole ratio of EDA to said alkyl 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 0.02-100% by weight of a suitable hydrocarbon 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 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 alkyl 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 hydrocarbon solvent; (g) azeotropically fractionally distilling a combination of said mother liquor from step (e) plus recovered 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 hydrocarbon solvent and recover said N-alkylethylenediamine.
10. A process according to Claim 9 wherein said hydrocarbon is n-heptane.
11. A process according to Claim 9 wherein step (a) is at a temperature of about 25°C to about 75°C.
12. A process according to Claim 9 wherein step ta) the mole ratio of EDA
to said alkyl halide is about 2-5 to 1.
to said alkyl halide is about 2-5 to 1.
13. A process according to Claim 9 wherein about 0.02-1.0% of said hydrocarbon, based on the weight of said reaction mixture is added in step (b).
14. A process according to Claim 10 wherein about 0.02-1.0% of said n-heptane, based on the weight of said reaction mixture, is added in step (b).
15. A process according to Claim 9 wherein the alkylizing agent of step (d) is about 50% aqueous sodium hydroxide.
16. A process according to Claim 11, 12 or 14 wherein said alkyl halide is an alkyl chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/048,337 US4217308A (en) | 1978-01-30 | 1979-06-14 | Process for preparing N-alkylethylenediamines |
| US48,337 | 1979-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1128070A true CA1128070A (en) | 1982-07-20 |
Family
ID=21954028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA332,700A Expired CA1128070A (en) | 1979-06-14 | 1979-07-27 | Process for preparing n-alkylethylene diamine |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPH0228588B2 (en) |
| BE (1) | BE877951A (en) |
| BR (1) | BR7904851A (en) |
| CA (1) | CA1128070A (en) |
| CH (1) | CH649075A5 (en) |
| DE (1) | DE2929841A1 (en) |
| FR (1) | FR2459224A1 (en) |
| GB (1) | GB2051040B (en) |
| IE (1) | IE48914B1 (en) |
| NL (1) | NL189039C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001267A (en) * | 1987-12-21 | 1991-03-19 | Texaco Chemical Company | Secondary alkyl amine derivatives of ethylenediamine |
| JP4532083B2 (en) * | 2003-07-28 | 2010-08-25 | 東ソー株式会社 | Method for producing N-monoalkyl-substituted alkyleneamine |
| JP4731915B2 (en) * | 2004-01-07 | 2011-07-27 | 大日本住友製薬株式会社 | Method for producing methylurea compound |
| EP2487151B1 (en) * | 2008-10-06 | 2015-09-02 | Dow Global Technologies LLC | Process for separating alkylethyleneamine(s) from ethyleneamine(s) compositions |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1129160B (en) * | 1959-06-04 | 1962-05-10 | Basf Ag | Process for the separation of ethylene diamine and water |
| DE1130814B (en) * | 1959-12-03 | 1962-06-07 | Basf Ag | Process for the continuous dewatering of ethylene diamines |
| DE2113208C3 (en) * | 1971-03-18 | 1974-04-25 | Th. Goldschmidt Ag, 4300 Essen | Octylamine derivatives, their manufacture and use as bio silk |
| SE381867B (en) * | 1973-03-07 | 1975-12-22 | Mo Och Domsjoe Ab | WAY TO REMOVE WATER FROM A MIXTURE OF ETHYLENDIAMINE AND WATER |
| DE2455678C3 (en) * | 1974-11-25 | 1979-05-10 | Bayer Ag, 5090 Leverkusen | Process for the production of tetramethylethylenediamine |
| IL56176A (en) * | 1978-01-30 | 1982-03-31 | American Cyanamid Co | Process for preparing n-ethylethylenediamine |
-
1979
- 1979-07-23 DE DE19792929841 patent/DE2929841A1/en active Granted
- 1979-07-25 FR FR7919187A patent/FR2459224A1/en active Granted
- 1979-07-27 CA CA332,700A patent/CA1128070A/en not_active Expired
- 1979-07-27 NL NL7905836A patent/NL189039C/en not_active IP Right Cessation
- 1979-07-27 GB GB7926360A patent/GB2051040B/en not_active Expired
- 1979-07-27 BE BE0/196503A patent/BE877951A/en not_active IP Right Cessation
- 1979-07-27 BR BR7904851A patent/BR7904851A/en not_active IP Right Cessation
- 1979-07-27 CH CH699179A patent/CH649075A5/en not_active IP Right Cessation
- 1979-08-08 IE IE145179A patent/IE48914B1/en not_active IP Right Cessation
-
1980
- 1980-06-13 JP JP7916380A patent/JPH0228588B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| GB2051040A (en) | 1981-01-14 |
| BE877951A (en) | 1980-01-28 |
| DE2929841A1 (en) | 1980-12-18 |
| NL7905836A (en) | 1980-12-16 |
| FR2459224B1 (en) | 1984-06-15 |
| DE2929841C2 (en) | 1989-11-09 |
| GB2051040B (en) | 1983-10-12 |
| JPH0228588B2 (en) | 1990-06-25 |
| IE791451L (en) | 1980-12-14 |
| JPS5645442A (en) | 1981-04-25 |
| BR7904851A (en) | 1981-01-27 |
| CH649075A5 (en) | 1985-04-30 |
| IE48914B1 (en) | 1985-06-12 |
| NL189039C (en) | 1992-12-16 |
| FR2459224A1 (en) | 1981-01-09 |
| NL189039B (en) | 1992-07-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |