CA2117007A1 - Process for the preparation of tertiary dialkylpolyhydroxy-amines - Google Patents
Process for the preparation of tertiary dialkylpolyhydroxy-aminesInfo
- Publication number
- CA2117007A1 CA2117007A1 CA 2117007 CA2117007A CA2117007A1 CA 2117007 A1 CA2117007 A1 CA 2117007A1 CA 2117007 CA2117007 CA 2117007 CA 2117007 A CA2117007 A CA 2117007A CA 2117007 A1 CA2117007 A1 CA 2117007A1
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- CA
- Canada
- Prior art keywords
- amine
- tertiary
- aldehyde
- employed
- bar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/12—Acyclic radicals, not substituted by cyclic structures attached to a nitrogen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
Abstract
Abstract Process for the preparation of tertiary dialkylpoly-hydroxy-amines In the process described a secondary N-monoalkylpoly-hydroxy-amine is reacted with an aldehyde in a molar ratio of 1 : from 0.9 to 1.5 in water as solvent and in the presence of a metallic hydrogenation catalyst at a hydrogen pressure of from 10 to 150 bar and at a tempera-ture of from 70 to 150°C, preferably in two reaction steps, to give the tertiary dialkylpolyhydroxy-amine.
Using the process according to the invention, tertiary polyhydroxy-amines, preferably in the form of di-C1 to C6-alkylglycamines, are obtained in a high yield and purity.
Using the process according to the invention, tertiary polyhydroxy-amines, preferably in the form of di-C1 to C6-alkylglycamines, are obtained in a high yield and purity.
Description
` ` 2~17007 ,~
H013C~IST A~CTIENGESELhSCHAFT HOE 93/F 909 Dr.GL-nu Werk Gendor~
Proaeæs for the preparation of tertiary dialkylpoly-hydroxy-amines Description Tertiary dialkylpolyhydroxy-amines, in particular in the i form of dialkylglycamines such as dimethylglucamina, are compounds which are valuable, for example, a~ an additive to wetting agents and cleaning agents, to plasticizers, and to slip additi~es and lubricant~ and the like. In accordance with US Patent 2,016,962, they are prepared by reacting a reduaing sugar such as gluco3e, fructose, lactose or xylose with a dialkylamine under hydrogenating condition~. The specific procedure i~ to react a sugar compound with a dialkylamine in water as ~ol~ent and in the presence o~ a supported ~ickel cataly~k at a hydrogen pres~ure of at lea~t 15 bar and a t~mperature of from 80 to 125C, to give the dialkylpolyhydroxy-amine. This process ~i.e. the reductive alkylation of ~ugar compounds with a dial~ylamine~ haa been known for a long time and ha~ the disadvantage that the tertiary ~ugar amine iR
generally obtained in a low yield.
- ' -:
The linear dialkylpolyhydroxy-amines under di~cussion, e~pecially in the form of dialkylglycamines or dialkyl-glucamines, have become o~ increasing importance inrecent time~, sinca they are biodegradable and can be obtained from sugar a~ a regener~tive raw material. There i3 therefore a more pressing requirement for a process by which the~e amino alcohols are obtained in a high yiald ~`~ 30 and purity. The present invantion provides such a process.
The proce~s according to the in~ention for the prepara-tio~ of a tertiary dialkylpolyhydroxy-amine comprises reacting a secondary N-monoalkylpolyhydroxy-amine with an aldeh~de in a molar ratio of 1 : from 0.90 to 1.5, i - 2 - 2117~07 ;, pre~erably 1 : from 1.03 to 1.1, in water as sol~ent and in the presence of a metallic hydrogenation c~talyst at a hydrogen pressure o~ from 10 to 150 bar, pra~erably ~rom 30 to 100 bar, and at a temperature of from 70 to 150C, preferably from 80 to 130C, to give the tertiary dialkylpolyhydroxy-amine.
In a preferred proce~ure~ the reaction is carried out in two steps in which a~ a secondary N-monoalkylpolyhydroxy-amine i~ ~irst reacted with an aldehyde in a molar ratio of 1 : from 0.90 to 1.5, preferably 1 : from 1.03 to 1.1, in water as sol~e~t at a temperature of from 15 to 60C, preferably from 20 to 40C, and at atmo~-pheric pres~ure to give the N-monoalkylpolyhydroxy-~ 15 amine/aldehyde adduct, and i b) the rsaction product obtained in step a) (essen-tially compri~ing the adduct formed and water) is hydrogenated in the presence of a metallic hydro-genation catalyst with hydrogen at a pressure of from 10 to 150 bar, preferably from 30 to 100 bar, and at a temperature of from 70 to 150C, preferably from 80 to 130C, to give the tertiary dialkylpoly-hydroxy-amine.
~he water, as solvent, i8 generally ~mployed in an amo~nt such that a from 5 to 60% strength by weight solution ia preseut, preferably a from 15 to 40% ~trength by w~ight solution, bas~d on the quantity of N-monoalkyl-¦ polyhydroxy-amine employed. The ~tated amount of water include~ water introduced by, for example, using formal-dehyde in the form- of a preferably from 30 to 40%
strength by we~ght aqueou~ solution. The metallic hydro-genation catalyst i8 preferably a palladium, platinum and/or nickel catalyst, with nickel catalysts being preferred. The hydrogenation catalyst can be employed as a ~upported catalyst, powder catalyst or Raney ~ickel catalyst. Raney nickal catalysts are preferred. The hydrogenatlon cataly~t i~ generally employed in an amount ~ 2117007 ~ of from 0.1 to 10% by weight, preferably in an amount of j from 0.5 to 5% by weight, based on N-monoalkylpoly-¦ hydroxy-ami~e Ifor clarity, the weight perce~tages stated ~ relate to the metal alo~e and thus do not also COMpriSe, -' 5 for example, the support material).
Specifically, the reaction according to the invention i pref~rably carried out by heating the N-monoalkylpoly-hydroxy-amine and water at atmospheric pressure to ~rom j 15 to 60C, preferably from 20 to 40~. The aldehyde ;¦ 10 compound i8 then added to this solution, continuously or in portions, while stirring and maintaining the stated ¦ temperature, a~d the mixture is then allowed to react to completion (adduct ~orma~ion) at from 15 to 60C, prefer-ably from 20 to 40C (0.5 to 2 hour~0 The resulting reaction product, essentially compri~ing th2 adduct ~ormed and water, i then subjected to hydrogenation. For thi~ purpose it is charged, together with the-hydroge~a-tion catalyst, while ~tirring, at a temperature of from 70 to 150C, preferably 80 to 130C, with hydrogen up to a pre~sure of ~rom 10 to 150 bar, preferably from 30 to 100 bar. This hydrogen pre~surQ i~ maintained at tha stated temperature and while stirring u~til no further hydrogen i8 taken up, which generally takes from 1 to 5 hour3 including any after-reaction. The re ulting reaction product essentially compris2s the desired tertiary dialkylpolyhydroxy-amine and water. If it is desired to isolate the tertiary amine compound ~rom the aqueous solution, then the catalyst and the water will be separated, thu~ gi~ing the tertiary amine compound, if 30 j desirQd by recrystallization ~rom a ~uitable sol~ent ~uch as isopropanol. The separation mentioned can be carried out by, for example, filtering and stripping or distillation.
..
The proces~ according to the invention provides the tertiary dialkylpolyhydroxy-amines in a high yield and purity. It can be carried out either continuou~ly or batchwi~.
~' ~
~ 21170~
; - 4 -The following comments apply with regard to the starting compound~: the aldehyde compound is preferably an alipha-~ic aldehyde, for example formaldehyde or acstaldehyde, with ~ormaldehyde being preferred. Formald~hyde is preferably employed in the form of a Erom 30 to 40%
strength by weight aqueous Qolution. The N-monoalk~1-, polyhydroxy-amine, often ~i~nply termed a secondary j polyhydroxy-amine, i8 pre~erably of the following formula (1) . 10 R~ z ( 1 ) 1 in which R1 i8 a C1 to C18 alkyl, preferably C1 to C6 alkyl J~ or Cl to C6 hydroxyalkyl ~uch a~ 2-hydxoxyathyl or 2-hydroxypropyl, a~d iR particularly pre~erably methyl or ethyl, and Z i~ a polyhydro~y hydrocarbon radical having a linear hydrocarbon chain with at least 3 OH
group~ or an alkoxylat2d derivati~e thereo~, preferably an ethoxylated and/or propoxylated derivati~e. Z i~
pr~erab1y the radical of a mono-, oligo- or polysac-charide compound which is connected to the nitrogen atom via a methylene group. Z i8 particularly preferably a group of the formula -CH2-CH(OH)~-CH~OH, in which n is an integer from 3 to 5, preferably 3 or 4 and particularly preferably 4. Ths ~tarting compounds of the ~ormula ll) are known and are commercially available. ~-i 25 The tertiary polyhydroxy-amines prepared by the process according to the in~e~tion are consequently of the ¦ following formula (2 Rl N-Z (2?
in which R1 a~d Z have the meanings gi~en and R2 i8 the substituent introduc~d by the aldehyde co~pound. It follows from the above statement~ that the di-C1 to C6-alkylglycamine~ are the pre~erred compounds, with the ` ` 21117~07 .....
. - 5 -glucamine compounds ~uch as dimethylglucamine, diethyl-i glucamine and ethylmethylgluca~ine being particularly :~
i3 preferred. .
The invention is now described in more detail using examples.
Example 1 ' .
; 288.7 g of a 36.5~ atrength by weight aqueous ~o~m-j aldehyde solution are metered into 1500 g of a 43%
~3 strength by weight aqueous N-methylglucami~e solution 10 (ami~e No. 22.3) ~t about 15C. The mixture i8 ~tirred at ~: about 15C for 1 hour and then 2R g of Ra~ey nickel are 3 added, and the mixture i8 hydrogenated at 100C a~d ~! 30 bar hydrogen pressure.
.
Yield of N,N-dimethylglucamine: 98.2~; m~lting point:
90C.
¦ Example 2 ' 288.7 g of a 36.5% s~rength by weight aqueous form-. ~ aldehyde solution are metered into 1500 g o~ a 43%
strength by weight aqueous N-methylglucamine solution : 20 (amine No. 22.3) at about 35C, and directly after the : additio~ has been completed the mixture is admixed with 28 g o~ Raney nickel and hydrogenatéd at 100C and 30 bar hydrogen preasure.
Yield of N,N-dimethylglucamine: 98.1%; melting poi~t:
25 89C. . `:
: .:
Example 3 288.7 g o~ a 36.5~ strength by weight aqueous ~orm-aldehyde solution are metered into 1500 g o a 43%
JI stre~gth by wPight a~ueous N-methylglucamine solution J 30 (amine No. 22.3) at about 35C. The mixture is sti~red at 1.
l``
- 6 - 2~7007 about 35C for 1 hour and then 28 g of Ran~y ~ickel are added, and the mi~tuxe i~ hydrogenated at 130C and 100 bar hydrogen pressure.
Yield of N,N-dimethylglucami~e: 97.8%; meltiny point:
90C.
Example 4 132 g o~ a 36.5% ~trength by weight aqueous ~ormaldehyde ~olution are metexed into a mixture of 689 g of a 43%
~trength by weight aqueou~ N-methylglucami~e ~olution (amine No. 22.3) and 811 g of additional water at about 35C. The mixture i8 stirred at about 35C $or 1 hour and the~ 28 g o~ Raney ~ickel are added, and the mixture is hydrogenated at 100C and 30 bar hydrogen pres~ure.
I .. - . . ~.
i Yield of N,N-dimethylglucamine: 97.8%; melti~g point:
99C.
Exampls 5 288.7 g o~ a 36.5~ strength by weight aqueous ~orm-aldehyde ~olution are metered into 1500 g of a 43%
strength by weight aqueous N-mathylglucamine ~olution 1 20 (amine No. 22.3) at 60C. The mixture is ~tirred at about ¦ 60~ ~or 1 hour and then 28 g o~ Raney niakel ar~ added, and the mixture i8 hydrogenated at 100C and 30 bar hydrogen pressure.
Yield of N,N-dimethylglucamine: 98.4%; melting point:
9~~
~xample 6 40 g of N-butylglucamine (amine No. 41.9) are ~u~pended in 60 g o~ water. 1~. 8 g of a 36.5% ~trength by weight aqueous formaldeh~de ~olu~ion are added to th~ ~uspen~io~
at about 25C. A clear solution i~ ~ormed which i~
9 ~ 7 , - 7 _ '~ stirred for a further 1 hour at about 25C. 1.7 g o~
~ Raney nickel i~ then added to the ~olution, a~d the :~
i mixture i~ hydrogenated at 100C and 30 bar hydrogen pr2. ~ure.
5 Yield o~ N-meth~l-N-butylgluc~ine: 99.3%; melting point: .
52C.
. .
¦ Example 7 ';
40 g of N-hexylglucamine (amil~e No. 37.93 are ~uspended in 60 g o water. 13.1 g of a 36.5% strength by weight :.
aqueou~ formaldehyde olution are added to the ~uspen~ion at 25C. A claar ~olution i8 formed w~iah i8 ~tirred for ..
I a further 1 hour at 25C. 1.9 g of Raney nickel i8 then added to the ~olution, and the mixture i~ hydrogenated at - 100C and 30 bar h~drogen pressure.
Yield of N-methyl-N-hexylglucamine: 99.2%; melting point:
74C.
...
~ . ~
.
. ~.
~ .
H013C~IST A~CTIENGESELhSCHAFT HOE 93/F 909 Dr.GL-nu Werk Gendor~
Proaeæs for the preparation of tertiary dialkylpoly-hydroxy-amines Description Tertiary dialkylpolyhydroxy-amines, in particular in the i form of dialkylglycamines such as dimethylglucamina, are compounds which are valuable, for example, a~ an additive to wetting agents and cleaning agents, to plasticizers, and to slip additi~es and lubricant~ and the like. In accordance with US Patent 2,016,962, they are prepared by reacting a reduaing sugar such as gluco3e, fructose, lactose or xylose with a dialkylamine under hydrogenating condition~. The specific procedure i~ to react a sugar compound with a dialkylamine in water as ~ol~ent and in the presence o~ a supported ~ickel cataly~k at a hydrogen pres~ure of at lea~t 15 bar and a t~mperature of from 80 to 125C, to give the dialkylpolyhydroxy-amine. This process ~i.e. the reductive alkylation of ~ugar compounds with a dial~ylamine~ haa been known for a long time and ha~ the disadvantage that the tertiary ~ugar amine iR
generally obtained in a low yield.
- ' -:
The linear dialkylpolyhydroxy-amines under di~cussion, e~pecially in the form of dialkylglycamines or dialkyl-glucamines, have become o~ increasing importance inrecent time~, sinca they are biodegradable and can be obtained from sugar a~ a regener~tive raw material. There i3 therefore a more pressing requirement for a process by which the~e amino alcohols are obtained in a high yiald ~`~ 30 and purity. The present invantion provides such a process.
The proce~s according to the in~ention for the prepara-tio~ of a tertiary dialkylpolyhydroxy-amine comprises reacting a secondary N-monoalkylpolyhydroxy-amine with an aldeh~de in a molar ratio of 1 : from 0.90 to 1.5, i - 2 - 2117~07 ;, pre~erably 1 : from 1.03 to 1.1, in water as sol~ent and in the presence of a metallic hydrogenation c~talyst at a hydrogen pressure o~ from 10 to 150 bar, pra~erably ~rom 30 to 100 bar, and at a temperature of from 70 to 150C, preferably from 80 to 130C, to give the tertiary dialkylpolyhydroxy-amine.
In a preferred proce~ure~ the reaction is carried out in two steps in which a~ a secondary N-monoalkylpolyhydroxy-amine i~ ~irst reacted with an aldehyde in a molar ratio of 1 : from 0.90 to 1.5, preferably 1 : from 1.03 to 1.1, in water as sol~e~t at a temperature of from 15 to 60C, preferably from 20 to 40C, and at atmo~-pheric pres~ure to give the N-monoalkylpolyhydroxy-~ 15 amine/aldehyde adduct, and i b) the rsaction product obtained in step a) (essen-tially compri~ing the adduct formed and water) is hydrogenated in the presence of a metallic hydro-genation catalyst with hydrogen at a pressure of from 10 to 150 bar, preferably from 30 to 100 bar, and at a temperature of from 70 to 150C, preferably from 80 to 130C, to give the tertiary dialkylpoly-hydroxy-amine.
~he water, as solvent, i8 generally ~mployed in an amo~nt such that a from 5 to 60% strength by weight solution ia preseut, preferably a from 15 to 40% ~trength by w~ight solution, bas~d on the quantity of N-monoalkyl-¦ polyhydroxy-amine employed. The ~tated amount of water include~ water introduced by, for example, using formal-dehyde in the form- of a preferably from 30 to 40%
strength by we~ght aqueou~ solution. The metallic hydro-genation catalyst i8 preferably a palladium, platinum and/or nickel catalyst, with nickel catalysts being preferred. The hydrogenation catalyst can be employed as a ~upported catalyst, powder catalyst or Raney ~ickel catalyst. Raney nickal catalysts are preferred. The hydrogenatlon cataly~t i~ generally employed in an amount ~ 2117007 ~ of from 0.1 to 10% by weight, preferably in an amount of j from 0.5 to 5% by weight, based on N-monoalkylpoly-¦ hydroxy-ami~e Ifor clarity, the weight perce~tages stated ~ relate to the metal alo~e and thus do not also COMpriSe, -' 5 for example, the support material).
Specifically, the reaction according to the invention i pref~rably carried out by heating the N-monoalkylpoly-hydroxy-amine and water at atmospheric pressure to ~rom j 15 to 60C, preferably from 20 to 40~. The aldehyde ;¦ 10 compound i8 then added to this solution, continuously or in portions, while stirring and maintaining the stated ¦ temperature, a~d the mixture is then allowed to react to completion (adduct ~orma~ion) at from 15 to 60C, prefer-ably from 20 to 40C (0.5 to 2 hour~0 The resulting reaction product, essentially compri~ing th2 adduct ~ormed and water, i then subjected to hydrogenation. For thi~ purpose it is charged, together with the-hydroge~a-tion catalyst, while ~tirring, at a temperature of from 70 to 150C, preferably 80 to 130C, with hydrogen up to a pre~sure of ~rom 10 to 150 bar, preferably from 30 to 100 bar. This hydrogen pre~surQ i~ maintained at tha stated temperature and while stirring u~til no further hydrogen i8 taken up, which generally takes from 1 to 5 hour3 including any after-reaction. The re ulting reaction product essentially compris2s the desired tertiary dialkylpolyhydroxy-amine and water. If it is desired to isolate the tertiary amine compound ~rom the aqueous solution, then the catalyst and the water will be separated, thu~ gi~ing the tertiary amine compound, if 30 j desirQd by recrystallization ~rom a ~uitable sol~ent ~uch as isopropanol. The separation mentioned can be carried out by, for example, filtering and stripping or distillation.
..
The proces~ according to the invention provides the tertiary dialkylpolyhydroxy-amines in a high yield and purity. It can be carried out either continuou~ly or batchwi~.
~' ~
~ 21170~
; - 4 -The following comments apply with regard to the starting compound~: the aldehyde compound is preferably an alipha-~ic aldehyde, for example formaldehyde or acstaldehyde, with ~ormaldehyde being preferred. Formald~hyde is preferably employed in the form of a Erom 30 to 40%
strength by weight aqueous Qolution. The N-monoalk~1-, polyhydroxy-amine, often ~i~nply termed a secondary j polyhydroxy-amine, i8 pre~erably of the following formula (1) . 10 R~ z ( 1 ) 1 in which R1 i8 a C1 to C18 alkyl, preferably C1 to C6 alkyl J~ or Cl to C6 hydroxyalkyl ~uch a~ 2-hydxoxyathyl or 2-hydroxypropyl, a~d iR particularly pre~erably methyl or ethyl, and Z i~ a polyhydro~y hydrocarbon radical having a linear hydrocarbon chain with at least 3 OH
group~ or an alkoxylat2d derivati~e thereo~, preferably an ethoxylated and/or propoxylated derivati~e. Z i~
pr~erab1y the radical of a mono-, oligo- or polysac-charide compound which is connected to the nitrogen atom via a methylene group. Z i8 particularly preferably a group of the formula -CH2-CH(OH)~-CH~OH, in which n is an integer from 3 to 5, preferably 3 or 4 and particularly preferably 4. Ths ~tarting compounds of the ~ormula ll) are known and are commercially available. ~-i 25 The tertiary polyhydroxy-amines prepared by the process according to the in~e~tion are consequently of the ¦ following formula (2 Rl N-Z (2?
in which R1 a~d Z have the meanings gi~en and R2 i8 the substituent introduc~d by the aldehyde co~pound. It follows from the above statement~ that the di-C1 to C6-alkylglycamine~ are the pre~erred compounds, with the ` ` 21117~07 .....
. - 5 -glucamine compounds ~uch as dimethylglucamine, diethyl-i glucamine and ethylmethylgluca~ine being particularly :~
i3 preferred. .
The invention is now described in more detail using examples.
Example 1 ' .
; 288.7 g of a 36.5~ atrength by weight aqueous ~o~m-j aldehyde solution are metered into 1500 g of a 43%
~3 strength by weight aqueous N-methylglucami~e solution 10 (ami~e No. 22.3) ~t about 15C. The mixture i8 ~tirred at ~: about 15C for 1 hour and then 2R g of Ra~ey nickel are 3 added, and the mixture i8 hydrogenated at 100C a~d ~! 30 bar hydrogen pressure.
.
Yield of N,N-dimethylglucamine: 98.2~; m~lting point:
90C.
¦ Example 2 ' 288.7 g of a 36.5% s~rength by weight aqueous form-. ~ aldehyde solution are metered into 1500 g o~ a 43%
strength by weight aqueous N-methylglucamine solution : 20 (amine No. 22.3) at about 35C, and directly after the : additio~ has been completed the mixture is admixed with 28 g o~ Raney nickel and hydrogenatéd at 100C and 30 bar hydrogen preasure.
Yield of N,N-dimethylglucamine: 98.1%; melting poi~t:
25 89C. . `:
: .:
Example 3 288.7 g o~ a 36.5~ strength by weight aqueous ~orm-aldehyde solution are metered into 1500 g o a 43%
JI stre~gth by wPight a~ueous N-methylglucamine solution J 30 (amine No. 22.3) at about 35C. The mixture is sti~red at 1.
l``
- 6 - 2~7007 about 35C for 1 hour and then 28 g of Ran~y ~ickel are added, and the mi~tuxe i~ hydrogenated at 130C and 100 bar hydrogen pressure.
Yield of N,N-dimethylglucami~e: 97.8%; meltiny point:
90C.
Example 4 132 g o~ a 36.5% ~trength by weight aqueous ~ormaldehyde ~olution are metexed into a mixture of 689 g of a 43%
~trength by weight aqueou~ N-methylglucami~e ~olution (amine No. 22.3) and 811 g of additional water at about 35C. The mixture i8 stirred at about 35C $or 1 hour and the~ 28 g o~ Raney ~ickel are added, and the mixture is hydrogenated at 100C and 30 bar hydrogen pres~ure.
I .. - . . ~.
i Yield of N,N-dimethylglucamine: 97.8%; melti~g point:
99C.
Exampls 5 288.7 g o~ a 36.5~ strength by weight aqueous ~orm-aldehyde ~olution are metered into 1500 g of a 43%
strength by weight aqueous N-mathylglucamine ~olution 1 20 (amine No. 22.3) at 60C. The mixture is ~tirred at about ¦ 60~ ~or 1 hour and then 28 g o~ Raney niakel ar~ added, and the mixture i8 hydrogenated at 100C and 30 bar hydrogen pressure.
Yield of N,N-dimethylglucamine: 98.4%; melting point:
9~~
~xample 6 40 g of N-butylglucamine (amine No. 41.9) are ~u~pended in 60 g o~ water. 1~. 8 g of a 36.5% ~trength by weight aqueous formaldeh~de ~olu~ion are added to th~ ~uspen~io~
at about 25C. A clear solution i~ ~ormed which i~
9 ~ 7 , - 7 _ '~ stirred for a further 1 hour at about 25C. 1.7 g o~
~ Raney nickel i~ then added to the ~olution, a~d the :~
i mixture i~ hydrogenated at 100C and 30 bar hydrogen pr2. ~ure.
5 Yield o~ N-meth~l-N-butylgluc~ine: 99.3%; melting point: .
52C.
. .
¦ Example 7 ';
40 g of N-hexylglucamine (amil~e No. 37.93 are ~uspended in 60 g o water. 13.1 g of a 36.5% strength by weight :.
aqueou~ formaldehyde olution are added to the ~uspen~ion at 25C. A claar ~olution i8 formed w~iah i8 ~tirred for ..
I a further 1 hour at 25C. 1.9 g of Raney nickel i8 then added to the ~olution, and the mixture i~ hydrogenated at - 100C and 30 bar h~drogen pressure.
Yield of N-methyl-N-hexylglucamine: 99.2%; melting point:
74C.
...
~ . ~
.
. ~.
~ .
Claims (10)
1. A process for the preparation of tertiary dialkyl-polyhydroxy-amines, which comprises reacting a secondary N-monoalkylpolyhydroxy-amine with an aldehyde in a molar ratio of 1 : from 0.9 to 1.5 in water as solvent and in the presence of a metallic hydrogenation catalyst at a hydrogen pressure of from 10 to 150 bar and at a temperature of from 70 to 150°C, to give the tertiary dialkylpolyhydroxy-amine .
2. The process as claimed in claim 1, which comprises employing the secondary N-monoalkylpolyhydroxy-amine and the aldehyde in a molar ratio of 1 : from 1.03 to 1.1 and reacting them at a hydrogen pressure of from 30 to 100 bar and at a temperature of from 80 to 130°C.
3. The process as claimed in claim 1, which comprises carrying out the reaction in two steps in which a) a secondary N-monoalkylpolyhydroxy-amine is first reacted with an aldehyde in a molar ratio of 1 : from 0.9 to 1.5 in water as solvent at a tem-perature of from 15 to 60°C and at atmospheric pressure to give the N-monoalkylpolyhydroxy-amine/aldehyde adduct, and b) the reaction product obtained in step a) is hydrogenated in the presence of a metallic hydro-genation catalyst with hydrogen at a pressure of from 10 to 150 bar and at a temperature of from to 150°C to give the tertiary dialkyl-polyhydroxy-amine.
4. The process as claimed in claim 3, wherein in step a) the secondary N-monoalkylpolyhydroxy-amine and the aldehyde are employed in a molar ratio of 1 : from 1.03 to 1.1 and are reacted at a tempera-ture of from 20 to 40°C to give the adduct, and in step b) the adduct is hydrogenated at a hydrogen pressure of from 30 to 100 bar and at a temperature of from 80 to 130°C.
5. The process as claimed in claim 1, wherein the hydrogenation catalyst employed is Raney nickel.
6. The process as claimed in claim 3, wherein the hydrogenation catalyst employed is Raney nickel.
7. The process as claimed in claim 1, wherein a secondary N-mono-C1 to C6-alkylglycamine and formaldehyde or acetaldehyde and, as metallic hydrogenation catalyst, Raney nickel are employed.
8. The process as claimed in claim 3, wherein a secondary N-mono-C1 to C6-alkylglycamine and formaldehyde or acetaldehyde and, as metallic hydrogenation catalyst, Raney nickel are employed.
9. The process as claimed in claims 1, wherein a secondary N-mono-C1 to C6-alkylglucamine and formaldehyde and, as metallic catalyst, Raney nickel are employed.
10. The process as claimed in claim 3, wherein a secondary N-mono-C1 to C6-alkylglucamine and formaldehyde and, as metallic catalyst, Raney nickel are employed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934307163 DE4307163A1 (en) | 1993-03-06 | 1993-03-06 | Process for the preparation of tertiary dialkyl polyhydroxyamines |
| DEP4307163.5 | 1993-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2117007A1 true CA2117007A1 (en) | 1994-09-07 |
Family
ID=6482175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2117007 Abandoned CA2117007A1 (en) | 1993-03-06 | 1994-03-04 | Process for the preparation of tertiary dialkylpolyhydroxy-amines |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0614881B1 (en) |
| JP (1) | JPH06340594A (en) |
| BR (1) | BR9400818A (en) |
| CA (1) | CA2117007A1 (en) |
| DE (2) | DE4307163A1 (en) |
| DK (1) | DK0614881T3 (en) |
| ES (1) | ES2109526T3 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10766853B2 (en) * | 2017-03-20 | 2020-09-08 | Clariant International Ltd | Catalytic process for preparing N,N-dimethylglucamine from N methylglucamine |
| US10772324B2 (en) | 2012-11-03 | 2020-09-15 | Clariant International Ltd. | Aqueous adjuvant-compositions |
| US10864275B2 (en) | 2012-05-30 | 2020-12-15 | Clariant International Ltd. | N-methyl-N-acylglucamine-containing composition |
| US10920080B2 (en) | 2015-10-09 | 2021-02-16 | Clariant International Ltd. | N-Alkyl glucamine-based universal pigment dispersions |
| US10961484B2 (en) | 2015-10-09 | 2021-03-30 | Clariant International Ltd. | Compositions comprising sugar amine and fatty acid |
| US11124855B2 (en) | 2011-07-21 | 2021-09-21 | Clariant International Ltd. | Binder composition for the agglomeration of fine minerals and pelletizing process |
| US11220603B2 (en) | 2016-05-09 | 2022-01-11 | Clariant International Ltd. | Stabilizers for silicate paints |
| US11425904B2 (en) | 2014-04-23 | 2022-08-30 | Clariant International Ltd. | Use of aqueous drift-reducing compositions |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060100127A1 (en) * | 2004-11-11 | 2006-05-11 | Meier Ingrid K | N,N-dialkylpolyhydroxyalkylamines |
| FR2947265B1 (en) * | 2009-06-25 | 2011-08-05 | Arkema France | PROCESS FOR THE PREPARATION OF ALKYLALCANOLAMINES |
| US10813862B2 (en) | 2012-05-30 | 2020-10-27 | Clariant International Ltd. | Use of N-methyl-N-acylglucamines as solubilizers |
| DE102014012020A1 (en) | 2014-08-13 | 2016-02-18 | Clariant International Ltd. | Low-VOC amines as a surface-active ingredient in dispersions |
| DE102014012022A1 (en) | 2014-08-13 | 2016-02-18 | Clariant International Ltd. | Organic ammonium salts of anionic pesticides |
| DE102015213123A1 (en) | 2015-07-14 | 2017-01-19 | Clariant International Ltd | N, N-dialkylglucamines for the stabilization of polymer dispersions |
| DE102016208486A1 (en) | 2016-05-18 | 2017-02-09 | Clariant International Ltd | Metalworking and hydraulic fluid |
| EP3601211B1 (en) * | 2017-03-20 | 2021-01-06 | Clariant International Ltd | Catalytic process for the manufacture of n,n-dimethylglucamin departing from n-methylglucamin |
| DE102020006798A1 (en) | 2020-11-05 | 2022-05-05 | Metall-Chemie Technologies Gmbh | Diethylaminosorbitol (DEAS) as a natural product-based neutralizing agent and surfactant |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH375332A (en) * | 1959-11-19 | 1964-02-29 | Geigy Ag J R | Process for the production of a new amino sugar |
| BE790119A (en) * | 1971-04-15 | 1973-04-13 | Basf Ag | PROCESS FOR THE PREPARATION OF SECONDARY OR TERTIARY ALIPHATIC AND CYCLOALIPHATIC AMINES. |
| US4190601A (en) * | 1978-05-31 | 1980-02-26 | Union Carbide Corporation | Production of tertiary amines by reductive alkylation |
| DE3471650D1 (en) * | 1983-11-22 | 1988-07-07 | Nippon Oils & Fats Co Ltd | Process for producing tertiary amines |
-
1993
- 1993-03-06 DE DE19934307163 patent/DE4307163A1/en not_active Withdrawn
-
1994
- 1994-03-01 ES ES94103024T patent/ES2109526T3/en not_active Expired - Lifetime
- 1994-03-01 DE DE59404497T patent/DE59404497D1/en not_active Expired - Fee Related
- 1994-03-01 EP EP19940103024 patent/EP0614881B1/en not_active Expired - Lifetime
- 1994-03-01 DK DK94103024T patent/DK0614881T3/en active
- 1994-03-04 CA CA 2117007 patent/CA2117007A1/en not_active Abandoned
- 1994-03-04 BR BR9400818A patent/BR9400818A/en not_active Application Discontinuation
- 1994-03-04 JP JP3469594A patent/JPH06340594A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11124855B2 (en) | 2011-07-21 | 2021-09-21 | Clariant International Ltd. | Binder composition for the agglomeration of fine minerals and pelletizing process |
| US10864275B2 (en) | 2012-05-30 | 2020-12-15 | Clariant International Ltd. | N-methyl-N-acylglucamine-containing composition |
| US10772324B2 (en) | 2012-11-03 | 2020-09-15 | Clariant International Ltd. | Aqueous adjuvant-compositions |
| US11425904B2 (en) | 2014-04-23 | 2022-08-30 | Clariant International Ltd. | Use of aqueous drift-reducing compositions |
| US10920080B2 (en) | 2015-10-09 | 2021-02-16 | Clariant International Ltd. | N-Alkyl glucamine-based universal pigment dispersions |
| US10961484B2 (en) | 2015-10-09 | 2021-03-30 | Clariant International Ltd. | Compositions comprising sugar amine and fatty acid |
| US11220603B2 (en) | 2016-05-09 | 2022-01-11 | Clariant International Ltd. | Stabilizers for silicate paints |
| US10766853B2 (en) * | 2017-03-20 | 2020-09-08 | Clariant International Ltd | Catalytic process for preparing N,N-dimethylglucamine from N methylglucamine |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2109526T3 (en) | 1998-01-16 |
| DE4307163A1 (en) | 1994-09-08 |
| JPH06340594A (en) | 1994-12-13 |
| EP0614881A1 (en) | 1994-09-14 |
| DK0614881T3 (en) | 1998-05-25 |
| EP0614881B1 (en) | 1997-11-05 |
| DE59404497D1 (en) | 1997-12-11 |
| BR9400818A (en) | 1994-11-01 |
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