CA1078382A - Production of bis-(n,n-disubstituted amino) compounds - Google Patents
Production of bis-(n,n-disubstituted amino) compoundsInfo
- Publication number
- CA1078382A CA1078382A CA253,205A CA253205A CA1078382A CA 1078382 A CA1078382 A CA 1078382A CA 253205 A CA253205 A CA 253205A CA 1078382 A CA1078382 A CA 1078382A
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- Prior art keywords
- alkyl
- diol
- group
- accordance
- phosphorus
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Abstract
PRODUCTION OF BIS-(N,N-DISUBSTITUTED AMINO) COMPOUNDS
(D#75,009-1-F) Abstract of the Disclosure An improved process is disclosed for selectively producing a bis(N,N-disubstituted amino) compound which includes contacting an (N,N-disubstituted) amine compound with a diol compound in the presence of a catalytically effective amount of a phosphorus-containing substance at a temperature of from about 250°C to 350°C under a pressure sufficient to maintain the mixture substantially in liquid phase and recovering from the resultant reaction mixture the bis-(N,N-disubstituted amino) compound.
(D#75,009-1-F) Abstract of the Disclosure An improved process is disclosed for selectively producing a bis(N,N-disubstituted amino) compound which includes contacting an (N,N-disubstituted) amine compound with a diol compound in the presence of a catalytically effective amount of a phosphorus-containing substance at a temperature of from about 250°C to 350°C under a pressure sufficient to maintain the mixture substantially in liquid phase and recovering from the resultant reaction mixture the bis-(N,N-disubstituted amino) compound.
Description
Background of the Invention Field of the Invention _.
The instant invention generally relates to an improved process for producing bis-(N,N-disubstituted amir.o) compounds such as bis-(N,N-dimethylamino)ethane or bis-(morpholino ethyl)ether directly from a diol and a secondary amine compound; and more particularly, to an improved selective liquid phase process for directly producing certain bis-(N,N-disubstituted amino) compound in the presence of certain specific catalytically effective substances.
Prior Art Bis-(N,N-disubstituted amino) compounds such as the alkanes, ethers and the like are generally well-known compounds having established utility as polyurethane catalysts. For 1~7838Z
example, bis-(morpholino-N-alkyl)ethers generally have established utility as polyurethane catalysts. The entire class of these ether compounds is useful in catalyzing urethane systems, including the C-alkyl substituted bis-(morpholino-N-alkyl)ether compounds ~herein one or both of the morpholine .
moieties contain C-(substituted) alkyl radicals on one or more of the carbon atoms and/or ~herein the N-alkyl moiety is either a branched or straight chain divalent radical.
The N,N'-dimorpholino alkanes are also generally useful in catalyzing urethane systems including the corresponding C-alkyl substituted compounds.
Bis-(N,N-disubstituted amino) compounds such as the bis-(N,N-disubstituted amino) alkanes have generally been prepared by methods involving halogenated reactants or intermediates. For example, in one method, N-(2-chloroethyl) morpholine is reacted ~ith morpholine. Such methods of prepara-tion are unsatisfactory in that the halogenated reactants are not readily available, and the methods involve caustic neutralization of the product and the concomitar.t disposal of polluting by-products, such as the alkali halide salts.
Additionally, the bis-(N,N-disubstituted) ethers such as bis-(morpholino-N-alkyl)ethers have been prepared by many methods. Examples of some of the more ~ell-known methods are disclosed in U. S. Patent No. 3,787,354. In one method .. ~ . . . . .. .
10783~Z
for bis-(morpholinoethyl)ether synthesis, N-(2-chloro-ethyl)morpholine is reacted with N-(2-hydroxyethyl)- ~
morpholine (HEM) and sodium. See, for example, J. Amer. Chem. -Soc., 62, 1448 (1940) and Acta Chem. Scand., 8, 350 (1954).
Another method involves the reaction of triethanolamine in the presence of hydrochloric acid. See, for example, J. Pharm.
Soc. Japan, 75, 1367 (1955). Still another method involves the reaction of morpholine with bis-(2-chloroethyl)ether. See, for example, Bull. Soc. Chim. France, 3537 (1965). As mentioned above, many of these processe s involve caustic neutralization with atter.dant problems~ Ir. addition, these methods involve the ;
use of chemical intermediates which are difficult to obtain and/or produce the desired product in low yield wherein the reaction product mixture contains by-products which are difficult to separate by known methods.
In addition, there are procedures described in the literature for preparing bis-(N,N-disubstituted amino) compounds in the presence of various catalysts. For example, ~;
it is disclosed in U. S. Patent No. 3,843,648 that N-amino-alkylated morpholines are produced by the cGndensation of N,N-dimethylaminoethanol and morpholine in vapor phase in the presence of AlP04 catalyst or a silica-alumina cracking oatalyst at temperatures of 200C to 400C.
Additionally, it has been disclosed that certain phosphoric acid compounds are effective as catalysts in promoting condensation reactions between some types of amines, and tertiary aminoalkanols. These reactions are carried out under 10t783~Z
:, ., relatively mild liquid phase processing conditions. For example, U. S. Patent No. 3,121,115 to Meuly teaches a ~-~
process for aminoalkylating certain amines having a replaceable amino hydrogen, particularly aromatic primary -~
and secondary amines, which includes heating the amine compourd with an N-tertiary aminoalkanol at from 150 C to -~
250 C in liquid phase with continuous water removal in the presence of a phosphoric acid compound such as aqueous or anhydrous orthophosphoric acid, phosphorus pentoxide or an alkyl phosphoric acid. However, the disc~osed process requires long reaction times.
Further, the corresponding bis-ethers are known to be produced in a vapor phase reaction with, for example, N-(2-hydroxyethyl)morpholine (HEM) in the presence of an lS activated alumina catalyst. See, for example, J. Amer. Chem.
Soc., 36, 298 (1941). This method suffers the attendant problems of vapor phase synthesis with low yields and extensive by-product formation.
Unexpectedly it has now been found that bis-(N,N-disubstituted amino) compounds can be selectively produced directly from the readily available corresponding N,N-disubstituted amine and a diol compound in liquid phase without the attendant deficiencies of previously knowr. processes. Under rigorous reaction conditions, i.e.
temperatures in the 250 C to 350 C range, the inventive process is surprisingly selective to the desired product.
The expected extensive decomposition and concomitant pro-- duction of unwanted side products is minimized. Additionally, the compounds effective in catalyzing the synthesis of th~
instant invention are readily available. The instant process does not require an expensive neutralization step nor is it attended by vapor phase reaction deficiencies such as vaporizing the reactants, low con~ersion rates, low selectivities, catalyst deactivation and the like. Additionally a diamine such as piperazine may be utilized as the amine compound to produce oligomeric products.
Summary of the Invention According to the broad aspect of the instant invention, a compound having at least one secondary amino group is reacted with a diol compound,and preferably an alkylene diol, in the presence of a catalytically effective amount of certain phosphorus-containing compounds at temperatures of from about 250C to about 350C at pressures sufficient to maintain the reactants and products in liquid phase.
The products selectively formed in practicing the instant invention can be depicted by the general formula:
~N-R-N ~
wherein R is the divalent hydrocarbon-containing nucleus of a diol, and each Rl and R2, independently, is an alkyl radical having from 1 to about 18 carbon atoms, or each pair, Rl and R2, ta~en together with the nitrogen atom to which each is attached, form a morpholino group, a p~perazino group, an N'-(s~bst~tu~ed) piperazino group, a C-alkyl substituted morpholino group, a (C-alkyl substituted) piperazino group, or an tN-substituted) (C-alkyl substituted) piperazino group.
.. .. ... . . . . .
AL-26~7-1 ; ` 107838Z
In accordance with one aspect of the invention, bis-(morpholino-N-alkyl)ether compounds are selectively produced directly from morpholine and an oxydialkanol compound in a catalyzed reaction process which includes initially con-tacting the reactants in the presence of a catalyticallyeffective amount of certain phosphorus-containing substances at temperatures of from about 250C to 350C while reaction pressures sufficient to retain the mixture substantially in liquid phase are maintained.
In a preferred embodiment, a bis-(morpholino-d,~-alkane compound is selectively produced by use of morpholine and the corresponding alkylene diol in accordance with the inventive process.
Description of the Preferred Embodiments In accordance with the inventive process, the bis-(N,N-disubstituted amino) compounds produced are the result of a trimolecular di-dehydration of an N,N-disubstituted amine, such as morpholine, and a diol, such as an alkylene diol, a;
dialkanolamine, an N-(alkyl~dialkanolamine, an oxydialkanol and the like. Thus, by varying the nucleus of the diol, one can achieve9 for example, the corresponding bis-(N,N-disubstituted amino)alkane compound, the bis-(N,N-disubstituted~
N-alkyl)ether, or the bis-(N,N-disubstituted-N-alkyl)amine.
Additionally, the amine compound can contain two secondary amines in the same molecule, thus providing sites for- oligomeric addition. For example, piperazine and ethylene 1C~783~3Z
diol can form a corresponding polyethylene polyamine compound under appropriate reaction conditions in accordance with the invention.
The N,N-(disubstituted)amines which are useful in the practice of this invention can be generally characterized as secondary amines. These comp~unds can be depicted by the formula:
~R
HN
wherein each Rl and R2, independently, is an alkyl radical having from 1 to about 18 carbon atoms, or Rl and R2, taken together with the nitrogen atom to which each is attached form a morpholine group, a piperazine group, an N-substituted piperazine group, a C-alkyl substituted morpholine group, a piperazine group or an N-substituted C-alkyl substituted piperazine group. Illustrative amines include dimethylamine, diethylamine, dihexylamine, ethylpropylamine, morpholine, piperazine, 2-methylmorpholine, 2-ethylpiperazine, 2,6-dimethylmorpholine and the like.
Preferred NjN-(disubstituted~amines in the practice of this invention are those of the above formula wherein each R
and R2, independently, is an alkyl radical having from ab~ut
The instant invention generally relates to an improved process for producing bis-(N,N-disubstituted amir.o) compounds such as bis-(N,N-dimethylamino)ethane or bis-(morpholino ethyl)ether directly from a diol and a secondary amine compound; and more particularly, to an improved selective liquid phase process for directly producing certain bis-(N,N-disubstituted amino) compound in the presence of certain specific catalytically effective substances.
Prior Art Bis-(N,N-disubstituted amino) compounds such as the alkanes, ethers and the like are generally well-known compounds having established utility as polyurethane catalysts. For 1~7838Z
example, bis-(morpholino-N-alkyl)ethers generally have established utility as polyurethane catalysts. The entire class of these ether compounds is useful in catalyzing urethane systems, including the C-alkyl substituted bis-(morpholino-N-alkyl)ether compounds ~herein one or both of the morpholine .
moieties contain C-(substituted) alkyl radicals on one or more of the carbon atoms and/or ~herein the N-alkyl moiety is either a branched or straight chain divalent radical.
The N,N'-dimorpholino alkanes are also generally useful in catalyzing urethane systems including the corresponding C-alkyl substituted compounds.
Bis-(N,N-disubstituted amino) compounds such as the bis-(N,N-disubstituted amino) alkanes have generally been prepared by methods involving halogenated reactants or intermediates. For example, in one method, N-(2-chloroethyl) morpholine is reacted ~ith morpholine. Such methods of prepara-tion are unsatisfactory in that the halogenated reactants are not readily available, and the methods involve caustic neutralization of the product and the concomitar.t disposal of polluting by-products, such as the alkali halide salts.
Additionally, the bis-(N,N-disubstituted) ethers such as bis-(morpholino-N-alkyl)ethers have been prepared by many methods. Examples of some of the more ~ell-known methods are disclosed in U. S. Patent No. 3,787,354. In one method .. ~ . . . . .. .
10783~Z
for bis-(morpholinoethyl)ether synthesis, N-(2-chloro-ethyl)morpholine is reacted with N-(2-hydroxyethyl)- ~
morpholine (HEM) and sodium. See, for example, J. Amer. Chem. -Soc., 62, 1448 (1940) and Acta Chem. Scand., 8, 350 (1954).
Another method involves the reaction of triethanolamine in the presence of hydrochloric acid. See, for example, J. Pharm.
Soc. Japan, 75, 1367 (1955). Still another method involves the reaction of morpholine with bis-(2-chloroethyl)ether. See, for example, Bull. Soc. Chim. France, 3537 (1965). As mentioned above, many of these processe s involve caustic neutralization with atter.dant problems~ Ir. addition, these methods involve the ;
use of chemical intermediates which are difficult to obtain and/or produce the desired product in low yield wherein the reaction product mixture contains by-products which are difficult to separate by known methods.
In addition, there are procedures described in the literature for preparing bis-(N,N-disubstituted amino) compounds in the presence of various catalysts. For example, ~;
it is disclosed in U. S. Patent No. 3,843,648 that N-amino-alkylated morpholines are produced by the cGndensation of N,N-dimethylaminoethanol and morpholine in vapor phase in the presence of AlP04 catalyst or a silica-alumina cracking oatalyst at temperatures of 200C to 400C.
Additionally, it has been disclosed that certain phosphoric acid compounds are effective as catalysts in promoting condensation reactions between some types of amines, and tertiary aminoalkanols. These reactions are carried out under 10t783~Z
:, ., relatively mild liquid phase processing conditions. For example, U. S. Patent No. 3,121,115 to Meuly teaches a ~-~
process for aminoalkylating certain amines having a replaceable amino hydrogen, particularly aromatic primary -~
and secondary amines, which includes heating the amine compourd with an N-tertiary aminoalkanol at from 150 C to -~
250 C in liquid phase with continuous water removal in the presence of a phosphoric acid compound such as aqueous or anhydrous orthophosphoric acid, phosphorus pentoxide or an alkyl phosphoric acid. However, the disc~osed process requires long reaction times.
Further, the corresponding bis-ethers are known to be produced in a vapor phase reaction with, for example, N-(2-hydroxyethyl)morpholine (HEM) in the presence of an lS activated alumina catalyst. See, for example, J. Amer. Chem.
Soc., 36, 298 (1941). This method suffers the attendant problems of vapor phase synthesis with low yields and extensive by-product formation.
Unexpectedly it has now been found that bis-(N,N-disubstituted amino) compounds can be selectively produced directly from the readily available corresponding N,N-disubstituted amine and a diol compound in liquid phase without the attendant deficiencies of previously knowr. processes. Under rigorous reaction conditions, i.e.
temperatures in the 250 C to 350 C range, the inventive process is surprisingly selective to the desired product.
The expected extensive decomposition and concomitant pro-- duction of unwanted side products is minimized. Additionally, the compounds effective in catalyzing the synthesis of th~
instant invention are readily available. The instant process does not require an expensive neutralization step nor is it attended by vapor phase reaction deficiencies such as vaporizing the reactants, low con~ersion rates, low selectivities, catalyst deactivation and the like. Additionally a diamine such as piperazine may be utilized as the amine compound to produce oligomeric products.
Summary of the Invention According to the broad aspect of the instant invention, a compound having at least one secondary amino group is reacted with a diol compound,and preferably an alkylene diol, in the presence of a catalytically effective amount of certain phosphorus-containing compounds at temperatures of from about 250C to about 350C at pressures sufficient to maintain the reactants and products in liquid phase.
The products selectively formed in practicing the instant invention can be depicted by the general formula:
~N-R-N ~
wherein R is the divalent hydrocarbon-containing nucleus of a diol, and each Rl and R2, independently, is an alkyl radical having from 1 to about 18 carbon atoms, or each pair, Rl and R2, ta~en together with the nitrogen atom to which each is attached, form a morpholino group, a p~perazino group, an N'-(s~bst~tu~ed) piperazino group, a C-alkyl substituted morpholino group, a (C-alkyl substituted) piperazino group, or an tN-substituted) (C-alkyl substituted) piperazino group.
.. .. ... . . . . .
AL-26~7-1 ; ` 107838Z
In accordance with one aspect of the invention, bis-(morpholino-N-alkyl)ether compounds are selectively produced directly from morpholine and an oxydialkanol compound in a catalyzed reaction process which includes initially con-tacting the reactants in the presence of a catalyticallyeffective amount of certain phosphorus-containing substances at temperatures of from about 250C to 350C while reaction pressures sufficient to retain the mixture substantially in liquid phase are maintained.
In a preferred embodiment, a bis-(morpholino-d,~-alkane compound is selectively produced by use of morpholine and the corresponding alkylene diol in accordance with the inventive process.
Description of the Preferred Embodiments In accordance with the inventive process, the bis-(N,N-disubstituted amino) compounds produced are the result of a trimolecular di-dehydration of an N,N-disubstituted amine, such as morpholine, and a diol, such as an alkylene diol, a;
dialkanolamine, an N-(alkyl~dialkanolamine, an oxydialkanol and the like. Thus, by varying the nucleus of the diol, one can achieve9 for example, the corresponding bis-(N,N-disubstituted amino)alkane compound, the bis-(N,N-disubstituted~
N-alkyl)ether, or the bis-(N,N-disubstituted-N-alkyl)amine.
Additionally, the amine compound can contain two secondary amines in the same molecule, thus providing sites for- oligomeric addition. For example, piperazine and ethylene 1C~783~3Z
diol can form a corresponding polyethylene polyamine compound under appropriate reaction conditions in accordance with the invention.
The N,N-(disubstituted)amines which are useful in the practice of this invention can be generally characterized as secondary amines. These comp~unds can be depicted by the formula:
~R
HN
wherein each Rl and R2, independently, is an alkyl radical having from 1 to about 18 carbon atoms, or Rl and R2, taken together with the nitrogen atom to which each is attached form a morpholine group, a piperazine group, an N-substituted piperazine group, a C-alkyl substituted morpholine group, a piperazine group or an N-substituted C-alkyl substituted piperazine group. Illustrative amines include dimethylamine, diethylamine, dihexylamine, ethylpropylamine, morpholine, piperazine, 2-methylmorpholine, 2-ethylpiperazine, 2,6-dimethylmorpholine and the like.
Preferred NjN-(disubstituted~amines in the practice of this invention are those of the above formula wherein each R
and R2, independently, is an alkyl radical having from ab~ut
2 to about 4 carbon atoms?a morpholine group,or ~he C-alkyl substituted morpholines wherein the C-alkyl substituents are lower alkyl radicals such as methyl, ethyl and.the like.
.
1~7838Z
-~he diol compounds that can be used in accordance with the invention need only contain more than one primary or secondary hydroxy moiety wherein the remainder o~ the molecule is non-deleterious to the reaction. Generally, the diol compounds are of the formula OH - R- OH
wherein R is a hydrocarbon containing,divalent moiety which can consist of, for example, an alkylene radical, a dialkylene ether radical, or a dialkylene amine radical. Preferably, R is an alkylene radical of from 2 to about 5 carbon atoms and more preferably an n-ethylene radical.
Suitable phosphorus-containing substances which can be employed include, for example, acidic metal phosphates, phosphoric acid compounds and their anhydrides, phosphorous acid compounds and anhydrides~ alkyl or aryl phosphate esters~
alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous acids and phosphoric acids, alkali metal monosalts of phosphoric acid, the thioanalogs of the foregoing, and mixtures of any of the above.
More particularly, suitable acidic metal phosphates include boron phosphate, ferric phosphate, aluminum phosphate, etc.
Suitable phosphoric acid compounds include aqueous or anhydrous phosphoric acids such as orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, and condensed . ~. . . . . -.. . . . . .. . . .
~07838Z
phosphoric aclds such as polyphosphoric acids. Accordingly, an example of a suitable phosphorous acid is orthophosphorous acid.
In addition, any commercially available mono-, di-, or tri-alkyl or aryl phosphate or phosphite ester can be employed as the catalyst in the inventive process. Additionally, bis(phosphates) and secondary phosphate esters such as those disclosed in U. S. 3,869,526 and U. S. 3,869,527, respectively, can be used. Preferably, the lower alkyl esters are employed such as those having from 1 to about 8 carbon atoms per alkyl group. Preferred aryl esters contain from about 6 to about 20 carbon atoms and may include a phenyl group or alkyl-substituted phenyl group.
Further, suitable aïkyï or aryl substituLted phosphoric acids or phosphorous acids which may be em?loyed as a catalyst include alkyl phosphonic acids, aryl phosphonic acids, alkyl phosphinic acids and aryl phosphinic acids. Preferably, such acids include alkyl or aryl groups and ha~e from 1 to about 8 carbon atoms in each alkyl group and about 6 to about 20 carbon atoms in each aryl group.
Specific examples of alkyl and aryl substituted phos-phorous and phosphoric acids that may be used in accordance with the invention are phenylphosphinic, ethylphosphonic, phenylphosphonic, naphthaphosphonic, and methylphosphinic acids. Examples of the alkyl and aryl substituted phosphorous and phosphoric acid esters are methylphenyl phosphonate, dimethylphenyl phosphonate, methylphenyl phosphinate, ethyl naph~haphosphinate, and propylmethyl phosphonate.
.. - .. -... . .. . . .
1~7838Z
The above-mentioned phosphorus compounds are not intended to be exhaustive of those which may be employed as a catalyst material in the process of the present invention.
Those materials are set forth to specify types of phosphorus compounds that we have found to be particularly effective as catalysts. Yet, of the compounds and types of compounds mentioned, we especially prefer to~employ those that have been found to be most reactive under the processing conditions of the invention. These especially preferred compounds include boron phosphate, aqueous and anhydrous orthophosphoric acid, pol~phosphoric acid, aluminum phosphate, ferric phosphate, aqueous and anhydrous orthophosphorous acid, triethylphosphite, triethylphosphate, and diethylphosphite, to name a few. Only a catalytically effective amount of the pho~phbrus substance is required to effect the condensation reaction between the reactants resulting in the formation of essentially salt-free product in good yield.
The quantity of phosphorus compound employed as the catalyst ln the inventive process may vary widely, depending upon its reactiv~ty, the reactants present and particular processing conditions employed. Usually this catalytic amount is within the range of from about 0.01 to about 10.0 wt. %, based upon the amount of diol compound material present; and-preferably the catalyst is employed in an amount of from about 0.5 to about 5.0 wt. % based upon the amount of diol compound.
Any of the above-mentioned phosphorus compounds may be employed as the catalyst of the process either alone, in combination with one of the other mentioned phosphorus compounds, or in combination with acidic compounds such as boric acid and the like. These latter acid compounds are generally ineffective as catalysts by themselves in the inventive process.
According to a greatly preferred embodiment, an alkylene diol and morpholine are intimately contacted by admixing. The admixture is heated in the presence of the phosphorus-containing substance at a temperature of from about 250C to about 350C and preferably at a temperature of about 275C to about 325C, under a pressure sufficient to maintain the reactlon mass ~n liquid phase which normally ranges from about 200 to about 2,000 psig. The react~on is allowed to proceed at the temperature employed until the desired amount - of conversion is obtained. Preferably the reaction is carried out under such conditions for a time period sufficient to provide a total reactants con~ersion of from about 10% to about 75% which is usually within the range of about 0,5 to about 5.0 hours.
The alkylene diol and the morpholine are contacted for reaction at molar ratios of from about 1:1 to about 1:5.
Preferably, the morpholine compound i5 employed in excess, such a~ about 0.5 to about 0.33 moles of alkylene diol per mole of morpholine.
1~7838Z
Generally the process of the invention can be carried out batchwise or continuously employing well-known batch and continuous processing techniques and conventional processing apparatus. Where the process is carried out continuously, we prefer to employ space velocities of reactants of from about 0.1 to about 4.0, preferably from about 0.5 to 1.5, grams total reactants per milliliter of total reactor volume per hour.
In such continuous reaction processes, the above-described phosphorus-containing catalyst materials may be employed as a feed stream alone or admixed with a reactant feed stream, or they may be employed as a fixed bed catalyst in the continuous reactor system. Generally speaking, these fixed bed catalysts comprise the phosphorus-containing catalyst material supported on a material such as silica, silica-alumina, alumina, dia~omaceous earth, etc., con-ventionally employed as inert reactor packing materials.
Such fixed bed supported catalysts and procedures for their ; preparation are well-known in the art and many are readily available commercially.
It is not critical to control the amount of water of reaction present during the heating of reactants and catalyst, such as by removal thereof as it is formed.
Usually, we prefer to retain the water in the reaction zone and remove it from the reaction mass during recovery of the product.
\` ~0'7~38Z , The desired N,N-disubstituted amine compound may ~-be readily recovered from the reaction product mass by conven-tional procedures, such as distillation, without difficulty.
For example, the reaction product mass may be directly distilled, or initially filtered to remove a small amount of formed solids - ;
which usually are amine salt complexes of the phosphorus compound eatalyst, and then distilled.
It should be realized that when the diol compound is, for example, a diethanolamine, that cyclization to the corres-ponding bis-N,N'disubstitutedpiperazine compound is possible as a side reaction, resulting in a sacrifice in yield of the desired product. Accordingly, when these diol compounds or their eorresponding C-alkyl substituted homologs are utilized, a `
large excess of the secondary amine compound is preferred.
Additionally, as mentioned hereinbefore, when piperazine is utilized as the amine reagent, two secondary amine reaction sites are present on a single molecule. Thus polymerization to various polyamine compounds is possible. -~
While the concept of polyamine formation is within the scope of the invention, many times it is desired to form the bis- ;
(piperazino)alkane. In order to aecomplish this selectivity, the proeess of the instant invention is carried out wherein an exeess of piperazine is utilized at temperatures o~ 275C
to about 325C.
13 r ` ` 107838Z
, .
The invention will be further illustrated by the following specific examples, which are given by way of illustration and not as limitations on the scope of this invention.
Example I
To a l-liter stirred stainless steel autoclave was charged 261 g (3.0 moles) morpholine, 95 g (1.25 mole) 1,2-monopropylene diol, and 8 g (0.029 mole) aqueous 30% ortho-phosphorous acid. After the autoclave was purged with nitrogen and sealed the mixture was heated to 300 C and held for 2.0 hours under a pressure of 450-650 psig with continuous stirring. After cooling, the crude reaction mass was analyzed by gas-liquid chromatography which showed it contained on a lights-water free basis, area %, 48.7 morpholine, 10.3 monopropylene diol, and 24.3 area % of an unknown component.
The reaction product mixture was distilled employing a 1 x 12 inch Vigreux column and 82 g of a colorless liquid, b.p.
113-114C/1.8 mm was collected. Nuclear magnetic resonance (NMR) spectroscopy established the identity of the liquid collected as 1,2-di-(4-morpholino)propane.
Example II
Employing the general procedure and equipment of Example 1, 174 g (2 moles) of morpholine, 44 g (0.5 moles) of 2-butenediol-1,4 and 6 g (0.022 mole; 4.4 mole %) of 30%
phosphorous acid were charged into the autoclave and heated under a nitrogen atmosphere at 280 C and 500 psig for about . ~
~07838Z
1 hour. After cooling, the reaction mass was recovered and distilled. Upon distillation, unreacted morpholine and 50 g of a colorless liquid boiling at 148-150C/3 mm Hg were recovered. The colorless distillate was shown by 2~
5 analysis to be 1,4-bis (N-morpholino)-2-butene. The NMR
analysis was further verified by titration.
Example III
According to the general procedure and equipment of Example I, 261 g (3 moles) morpholine, 96 g (1.06 moles) of 1,3-butylene diol and 8 g (0.029 moles; 2.8 mole %) of 30% phosphorous acid were charged into the autoclave and heated under a nitrogen atmosphere for 2 hours at 300C and 425-615 psig. After cooling,the reaction nass was recovered and distilled into 5 fractions as listed in 15 Table I below.
TABLE I
Pressure, Fraction Grams mm B.p., C
. . _ 22 0.6 79-85 2 36 1.3 85
.
1~7838Z
-~he diol compounds that can be used in accordance with the invention need only contain more than one primary or secondary hydroxy moiety wherein the remainder o~ the molecule is non-deleterious to the reaction. Generally, the diol compounds are of the formula OH - R- OH
wherein R is a hydrocarbon containing,divalent moiety which can consist of, for example, an alkylene radical, a dialkylene ether radical, or a dialkylene amine radical. Preferably, R is an alkylene radical of from 2 to about 5 carbon atoms and more preferably an n-ethylene radical.
Suitable phosphorus-containing substances which can be employed include, for example, acidic metal phosphates, phosphoric acid compounds and their anhydrides, phosphorous acid compounds and anhydrides~ alkyl or aryl phosphate esters~
alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous acids and phosphoric acids, alkali metal monosalts of phosphoric acid, the thioanalogs of the foregoing, and mixtures of any of the above.
More particularly, suitable acidic metal phosphates include boron phosphate, ferric phosphate, aluminum phosphate, etc.
Suitable phosphoric acid compounds include aqueous or anhydrous phosphoric acids such as orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, and condensed . ~. . . . . -.. . . . . .. . . .
~07838Z
phosphoric aclds such as polyphosphoric acids. Accordingly, an example of a suitable phosphorous acid is orthophosphorous acid.
In addition, any commercially available mono-, di-, or tri-alkyl or aryl phosphate or phosphite ester can be employed as the catalyst in the inventive process. Additionally, bis(phosphates) and secondary phosphate esters such as those disclosed in U. S. 3,869,526 and U. S. 3,869,527, respectively, can be used. Preferably, the lower alkyl esters are employed such as those having from 1 to about 8 carbon atoms per alkyl group. Preferred aryl esters contain from about 6 to about 20 carbon atoms and may include a phenyl group or alkyl-substituted phenyl group.
Further, suitable aïkyï or aryl substituLted phosphoric acids or phosphorous acids which may be em?loyed as a catalyst include alkyl phosphonic acids, aryl phosphonic acids, alkyl phosphinic acids and aryl phosphinic acids. Preferably, such acids include alkyl or aryl groups and ha~e from 1 to about 8 carbon atoms in each alkyl group and about 6 to about 20 carbon atoms in each aryl group.
Specific examples of alkyl and aryl substituted phos-phorous and phosphoric acids that may be used in accordance with the invention are phenylphosphinic, ethylphosphonic, phenylphosphonic, naphthaphosphonic, and methylphosphinic acids. Examples of the alkyl and aryl substituted phosphorous and phosphoric acid esters are methylphenyl phosphonate, dimethylphenyl phosphonate, methylphenyl phosphinate, ethyl naph~haphosphinate, and propylmethyl phosphonate.
.. - .. -... . .. . . .
1~7838Z
The above-mentioned phosphorus compounds are not intended to be exhaustive of those which may be employed as a catalyst material in the process of the present invention.
Those materials are set forth to specify types of phosphorus compounds that we have found to be particularly effective as catalysts. Yet, of the compounds and types of compounds mentioned, we especially prefer to~employ those that have been found to be most reactive under the processing conditions of the invention. These especially preferred compounds include boron phosphate, aqueous and anhydrous orthophosphoric acid, pol~phosphoric acid, aluminum phosphate, ferric phosphate, aqueous and anhydrous orthophosphorous acid, triethylphosphite, triethylphosphate, and diethylphosphite, to name a few. Only a catalytically effective amount of the pho~phbrus substance is required to effect the condensation reaction between the reactants resulting in the formation of essentially salt-free product in good yield.
The quantity of phosphorus compound employed as the catalyst ln the inventive process may vary widely, depending upon its reactiv~ty, the reactants present and particular processing conditions employed. Usually this catalytic amount is within the range of from about 0.01 to about 10.0 wt. %, based upon the amount of diol compound material present; and-preferably the catalyst is employed in an amount of from about 0.5 to about 5.0 wt. % based upon the amount of diol compound.
Any of the above-mentioned phosphorus compounds may be employed as the catalyst of the process either alone, in combination with one of the other mentioned phosphorus compounds, or in combination with acidic compounds such as boric acid and the like. These latter acid compounds are generally ineffective as catalysts by themselves in the inventive process.
According to a greatly preferred embodiment, an alkylene diol and morpholine are intimately contacted by admixing. The admixture is heated in the presence of the phosphorus-containing substance at a temperature of from about 250C to about 350C and preferably at a temperature of about 275C to about 325C, under a pressure sufficient to maintain the reactlon mass ~n liquid phase which normally ranges from about 200 to about 2,000 psig. The react~on is allowed to proceed at the temperature employed until the desired amount - of conversion is obtained. Preferably the reaction is carried out under such conditions for a time period sufficient to provide a total reactants con~ersion of from about 10% to about 75% which is usually within the range of about 0,5 to about 5.0 hours.
The alkylene diol and the morpholine are contacted for reaction at molar ratios of from about 1:1 to about 1:5.
Preferably, the morpholine compound i5 employed in excess, such a~ about 0.5 to about 0.33 moles of alkylene diol per mole of morpholine.
1~7838Z
Generally the process of the invention can be carried out batchwise or continuously employing well-known batch and continuous processing techniques and conventional processing apparatus. Where the process is carried out continuously, we prefer to employ space velocities of reactants of from about 0.1 to about 4.0, preferably from about 0.5 to 1.5, grams total reactants per milliliter of total reactor volume per hour.
In such continuous reaction processes, the above-described phosphorus-containing catalyst materials may be employed as a feed stream alone or admixed with a reactant feed stream, or they may be employed as a fixed bed catalyst in the continuous reactor system. Generally speaking, these fixed bed catalysts comprise the phosphorus-containing catalyst material supported on a material such as silica, silica-alumina, alumina, dia~omaceous earth, etc., con-ventionally employed as inert reactor packing materials.
Such fixed bed supported catalysts and procedures for their ; preparation are well-known in the art and many are readily available commercially.
It is not critical to control the amount of water of reaction present during the heating of reactants and catalyst, such as by removal thereof as it is formed.
Usually, we prefer to retain the water in the reaction zone and remove it from the reaction mass during recovery of the product.
\` ~0'7~38Z , The desired N,N-disubstituted amine compound may ~-be readily recovered from the reaction product mass by conven-tional procedures, such as distillation, without difficulty.
For example, the reaction product mass may be directly distilled, or initially filtered to remove a small amount of formed solids - ;
which usually are amine salt complexes of the phosphorus compound eatalyst, and then distilled.
It should be realized that when the diol compound is, for example, a diethanolamine, that cyclization to the corres-ponding bis-N,N'disubstitutedpiperazine compound is possible as a side reaction, resulting in a sacrifice in yield of the desired product. Accordingly, when these diol compounds or their eorresponding C-alkyl substituted homologs are utilized, a `
large excess of the secondary amine compound is preferred.
Additionally, as mentioned hereinbefore, when piperazine is utilized as the amine reagent, two secondary amine reaction sites are present on a single molecule. Thus polymerization to various polyamine compounds is possible. -~
While the concept of polyamine formation is within the scope of the invention, many times it is desired to form the bis- ;
(piperazino)alkane. In order to aecomplish this selectivity, the proeess of the instant invention is carried out wherein an exeess of piperazine is utilized at temperatures o~ 275C
to about 325C.
13 r ` ` 107838Z
, .
The invention will be further illustrated by the following specific examples, which are given by way of illustration and not as limitations on the scope of this invention.
Example I
To a l-liter stirred stainless steel autoclave was charged 261 g (3.0 moles) morpholine, 95 g (1.25 mole) 1,2-monopropylene diol, and 8 g (0.029 mole) aqueous 30% ortho-phosphorous acid. After the autoclave was purged with nitrogen and sealed the mixture was heated to 300 C and held for 2.0 hours under a pressure of 450-650 psig with continuous stirring. After cooling, the crude reaction mass was analyzed by gas-liquid chromatography which showed it contained on a lights-water free basis, area %, 48.7 morpholine, 10.3 monopropylene diol, and 24.3 area % of an unknown component.
The reaction product mixture was distilled employing a 1 x 12 inch Vigreux column and 82 g of a colorless liquid, b.p.
113-114C/1.8 mm was collected. Nuclear magnetic resonance (NMR) spectroscopy established the identity of the liquid collected as 1,2-di-(4-morpholino)propane.
Example II
Employing the general procedure and equipment of Example 1, 174 g (2 moles) of morpholine, 44 g (0.5 moles) of 2-butenediol-1,4 and 6 g (0.022 mole; 4.4 mole %) of 30%
phosphorous acid were charged into the autoclave and heated under a nitrogen atmosphere at 280 C and 500 psig for about . ~
~07838Z
1 hour. After cooling, the reaction mass was recovered and distilled. Upon distillation, unreacted morpholine and 50 g of a colorless liquid boiling at 148-150C/3 mm Hg were recovered. The colorless distillate was shown by 2~
5 analysis to be 1,4-bis (N-morpholino)-2-butene. The NMR
analysis was further verified by titration.
Example III
According to the general procedure and equipment of Example I, 261 g (3 moles) morpholine, 96 g (1.06 moles) of 1,3-butylene diol and 8 g (0.029 moles; 2.8 mole %) of 30% phosphorous acid were charged into the autoclave and heated under a nitrogen atmosphere for 2 hours at 300C and 425-615 psig. After cooling,the reaction nass was recovered and distilled into 5 fractions as listed in 15 Table I below.
TABLE I
Pressure, Fraction Grams mm B.p., C
. . _ 22 0.6 79-85 2 36 1.3 85
3 23 1.0 85-92
4 20 1.8 92-128 48 1.8 128-137 Fractions 1-4 were shown by analysis to consist essentially of morpholinobutanol and predominantly 4-(N-morpholino)-2-butanol and 3-(N-morpholino) -l-butanol. The fifth fraction, i.e. that fraction having a boiling point of ~L~783~2 128-137C/1.8 mm Hg was shown by analysis to consist essentially of pure 1,3-bis (N-morpholino)butane.
Example IV
Employing the general procedllre and reaction equipment described in Example I, 262.0 g (3.0 moles) morpholine, 106.0 g (1.0 mole) oxydie~hanol and 11.4 g (0.1 mole~
85% orthophosphoric acid were heated, with stirring, at 300C for 3.0 hours under a pressure of 375-540 psig.
Analysis of the reaction product mass by gas-liquid chroma-tography (lights-water free basis, area ~/O) showed it contained 20.6 morpholine, 4.5 oxydiethanol, 9.6 hydroxyethoxyethyl-morpholine, 21.1 1,2-bis-(morpholino)ethane, 31.0 2,2'-dimorpholinodiethyl ether and 2.() heavies.
Example V
Employing the procedure described in Example I, a ser~es of runs were conducted to obtain 1,2-ethylenedipipera-zine employing varying amounts of piperazine and ethylene diol and various types and amounts of acidic phosphorus-containing compounds as catalyst, as set forth in the follow-ing Table II. In all runs the reactant-catalyst mixture was heated at a temperature of 290C under autogenous pres~ure for 2.0 hours. Conversion of ethylene diol was essentially complete in all cases. Gas-liquid chromatography analytical results of each reaction product are also set forth in the following Table II.
The results of Table II demonstrate the varied types of acidic phosphorus-containing compound~ that may be employed as a catalyst in the inventive process.
. ~ , ~ .. ., . . . .. . ~ . , .
1~7838Z
o ~n ~ W~ I~ lZ
~,- 1 t ~It ~tn ::~
~ O ~J-O I'-O iJ-O 1'-~- O
_ G~ n F ~ ~D ~ r P ~ ~
P- ~D ~ -~ oo O
O Q, ~ ~ IJ-'q o , , , ~-n P' G~
w i- w _ ~o ~- o o o o o ;3:
rD o o o o o o tt l--O ~ o ~ \--O ~ 1~ ~D
P- ~ ~ ~ O O U~
~D ~d X~
n ~
O ~ 1 0 0 tD N
U~ ~-r~ b~
e~
. I~ O C) H
O O O ~ O ~_ ~
O O ~O O tD ~-P~
N 1'- ~
. . . . . 1-.~ O
CO ~D O ~ o ~q ~ , r~
~ C~
~ :1' l~ ~ ~ ~_ ~I O O~ It (D _ ~1 ~1 ~ N (1~ 1--~;~ ~ '
Example IV
Employing the general procedllre and reaction equipment described in Example I, 262.0 g (3.0 moles) morpholine, 106.0 g (1.0 mole) oxydie~hanol and 11.4 g (0.1 mole~
85% orthophosphoric acid were heated, with stirring, at 300C for 3.0 hours under a pressure of 375-540 psig.
Analysis of the reaction product mass by gas-liquid chroma-tography (lights-water free basis, area ~/O) showed it contained 20.6 morpholine, 4.5 oxydiethanol, 9.6 hydroxyethoxyethyl-morpholine, 21.1 1,2-bis-(morpholino)ethane, 31.0 2,2'-dimorpholinodiethyl ether and 2.() heavies.
Example V
Employing the procedure described in Example I, a ser~es of runs were conducted to obtain 1,2-ethylenedipipera-zine employing varying amounts of piperazine and ethylene diol and various types and amounts of acidic phosphorus-containing compounds as catalyst, as set forth in the follow-ing Table II. In all runs the reactant-catalyst mixture was heated at a temperature of 290C under autogenous pres~ure for 2.0 hours. Conversion of ethylene diol was essentially complete in all cases. Gas-liquid chromatography analytical results of each reaction product are also set forth in the following Table II.
The results of Table II demonstrate the varied types of acidic phosphorus-containing compound~ that may be employed as a catalyst in the inventive process.
. ~ , ~ .. ., . . . .. . ~ . , .
1~7838Z
o ~n ~ W~ I~ lZ
~,- 1 t ~It ~tn ::~
~ O ~J-O I'-O iJ-O 1'-~- O
_ G~ n F ~ ~D ~ r P ~ ~
P- ~D ~ -~ oo O
O Q, ~ ~ IJ-'q o , , , ~-n P' G~
w i- w _ ~o ~- o o o o o ;3:
rD o o o o o o tt l--O ~ o ~ \--O ~ 1~ ~D
P- ~ ~ ~ O O U~
~D ~d X~
n ~
O ~ 1 0 0 tD N
U~ ~-r~ b~
e~
. I~ O C) H
O O O ~ O ~_ ~
O O ~O O tD ~-P~
N 1'- ~
. . . . . 1-.~ O
CO ~D O ~ o ~q ~ , r~
~ C~
~ :1' l~ ~ ~ ~_ ~I O O~ It (D _ ~1 ~1 ~ N (1~ 1--~;~ ~ '
5~ ~ ~h l~ ~ ~
00 ~ CO W ~I ~ (D
~_ `_ While the invention has been explained in relation to its preferred embodiment, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification and is intended to cover such modifications as fall within the scope of the appended claims.
.
00 ~ CO W ~I ~ (D
~_ `_ While the invention has been explained in relation to its preferred embodiment, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification and is intended to cover such modifications as fall within the scope of the appended claims.
.
Claims (8)
1. A mehod of producing an amine compound of the general formula:
wherein R is the divalent hydrocarbon-containing nucleus of a diol, and each R1 and R2, independently, is an alkyl radical having from 1 to about 18 carbon atoms, or each pair, R1 and R2, taken together with the nitrogen atom to which each is attached, form a morpholino group, a piperazino group, an N-(substituted) piperazino group, a (C-alkyl substituted) morpholino group, a (C-alkyl substituted) piperazino group, an (N-substituted) (C-alkyl substituted) piperazino group comprising the steps of:
contacting an amine compound having at least one secondary amino group with a diol compound in the presence of a catalytically effective amount of a phosphorus-containing compound at temperatures of from about 250°C to about 350°C at pressures sufficient to maintain the reactants and products in liquid phase; and, recovering from the resultant reaction product mixture said amine compound.
wherein R is the divalent hydrocarbon-containing nucleus of a diol, and each R1 and R2, independently, is an alkyl radical having from 1 to about 18 carbon atoms, or each pair, R1 and R2, taken together with the nitrogen atom to which each is attached, form a morpholino group, a piperazino group, an N-(substituted) piperazino group, a (C-alkyl substituted) morpholino group, a (C-alkyl substituted) piperazino group, an (N-substituted) (C-alkyl substituted) piperazino group comprising the steps of:
contacting an amine compound having at least one secondary amino group with a diol compound in the presence of a catalytically effective amount of a phosphorus-containing compound at temperatures of from about 250°C to about 350°C at pressures sufficient to maintain the reactants and products in liquid phase; and, recovering from the resultant reaction product mixture said amine compound.
2. The process in accordance with Claim 1 wherein said contacting is accomplished at a temperature of from about 275°C to about 325°C.
3. The process in accordance with Claim 1 wherein said contacting is accomplished at a pressure of from about 200 psig to about 2,000 psig.
4. The process in accordance with Claim 1 wherein said phosphorus-containing substance is selected from the group consisting of acidic metal phosphates, phosphoric acid and their anhydrides or phosphorous acids and their anhydrides, alkyl or aryl phosphate esters, alkyl or aryl phosphite esters, alkyl or aryl substituted phosphorous acid and phosphoric acid, alkali metal monosalts, phosphoric acid, the thioanalogs of the foregoing and mixtures thereof.
5. The process in accordance with Claim 4 wherein said phosphorus-containing substance is phosphorous acid.
6. The process in accordance with Claim 1 wherein said phosphorus-containing substance is present in an amount from about 0.01 to about 10.0 mole percent based on the amount of said diol present.
7. The process in accordance with Claim 6 wherein said phosphorus-containing substance is present in an amount from about 0.5 to about 5.0 weight percent based on the amount of diol present.
8. The process in accordance with Claim 1 wherein said diol is selected from a group consisting of an oxydialkanol, a dialkanolamine, and an alkylene diol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58302175A | 1975-06-02 | 1975-06-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1078382A true CA1078382A (en) | 1980-05-27 |
Family
ID=24331360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA253,205A Expired CA1078382A (en) | 1975-06-02 | 1976-05-25 | Production of bis-(n,n-disubstituted amino) compounds |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS51146403A (en) |
| BE (1) | BE842467A (en) |
| CA (1) | CA1078382A (en) |
| DE (1) | DE2624136A1 (en) |
| FR (1) | FR2313378A1 (en) |
| IT (1) | IT1063219B (en) |
| NL (1) | NL7605639A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0716084A1 (en) | 1994-12-09 | 1996-06-12 | Huntsman Corporation | Preparation of 4,4'-(oxydi-2,1-ethanediyl)bis-morpholine and hydroxyethoxyethyl morpholine |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2658728A1 (en) * | 1976-12-24 | 1978-06-29 | Bayer Ag | N-ALKYLATION OF AROMATIC AMINES |
| DE102010019116A1 (en) * | 2010-04-30 | 2011-11-03 | Bionical Systems Ag | Arrangement for mains isolation of a drive device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3121115A (en) * | 1960-05-02 | 1964-02-11 | Du Pont | Aminoalkylation of amines and phenols |
-
1976
- 1976-05-25 CA CA253,205A patent/CA1078382A/en not_active Expired
- 1976-05-26 NL NL7605639A patent/NL7605639A/en unknown
- 1976-05-28 DE DE19762624136 patent/DE2624136A1/en active Pending
- 1976-05-31 FR FR7616317A patent/FR2313378A1/en not_active Withdrawn
- 1976-06-01 IT IT2385476A patent/IT1063219B/en active
- 1976-06-01 JP JP51062986A patent/JPS51146403A/en active Pending
- 1976-06-01 BE BE167543A patent/BE842467A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0716084A1 (en) | 1994-12-09 | 1996-06-12 | Huntsman Corporation | Preparation of 4,4'-(oxydi-2,1-ethanediyl)bis-morpholine and hydroxyethoxyethyl morpholine |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2624136A1 (en) | 1976-12-23 |
| BE842467A (en) | 1976-12-01 |
| IT1063219B (en) | 1985-02-11 |
| FR2313378A1 (en) | 1976-12-31 |
| NL7605639A (en) | 1976-12-06 |
| JPS51146403A (en) | 1976-12-16 |
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