CA2105100A1 - Preparation of unsaturated amines - Google Patents
Preparation of unsaturated aminesInfo
- Publication number
- CA2105100A1 CA2105100A1 CA002105100A CA2105100A CA2105100A1 CA 2105100 A1 CA2105100 A1 CA 2105100A1 CA 002105100 A CA002105100 A CA 002105100A CA 2105100 A CA2105100 A CA 2105100A CA 2105100 A1 CA2105100 A1 CA 2105100A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- hydrogen
- alkylamino
- methyl
- mol
- 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
- 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
- C07D295/027—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 containing only one hetero ring
- C07D295/03—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 containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
- C07C209/26—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
-
- 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
-
- 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
- C07D295/12—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 or doubly bound nitrogen atoms
- C07D295/125—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 or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—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 or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the disclosure: a process for preparing unsaturated amines of the general formula I
(I), where R1,R2,R3,R4,R5 are hydrogen, C1- to C20-alkyl, C2- to C20-a1kenY1, C3- to C8-cycloalkyl, C3- to C8-cycloalkenyl, phe~nyl, C7- to C20-phenyl-alkyl, C1- to C20-alkoxy, phenoxy, C7- to C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino, C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or R1 and R2 or R1 and R3 or R2 and R3 together are a C2- to C8-alkylene which is unsubtituted or monosubstituted to pentasubstituted by C1-to C4-alkyl or unsubstituted or monosub-stituted to tetrasubstituted by amino, N-C1- to C8-alkylamino, N,N-C1- to C8-di-alkylamino, hydroxyl, O-C1- to C8-alkyl-amino and/or C1- to C8-alkoxycarbonyl, and X is =C-N(R4R5) or -C=N-R4, by reacting 2-alkenals of the general formula II
(II), where R1, R2 and R3 have the abovementioned meanings, with primary or secondary amines of the general formula III
( III ), where R4 and R5 have the abovementioned meanings, at from (-20) to 70°C and pressures from 0.01 to 100 bar, by carrying out the reaction without removing the water of reaction and transaminating the product to give the compounds I' and hydrogenating the latter to give novel 1,3-diamines of the general formula IV
(IV),
(I), where R1,R2,R3,R4,R5 are hydrogen, C1- to C20-alkyl, C2- to C20-a1kenY1, C3- to C8-cycloalkyl, C3- to C8-cycloalkenyl, phe~nyl, C7- to C20-phenyl-alkyl, C1- to C20-alkoxy, phenoxy, C7- to C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino, C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or R1 and R2 or R1 and R3 or R2 and R3 together are a C2- to C8-alkylene which is unsubtituted or monosubstituted to pentasubstituted by C1-to C4-alkyl or unsubstituted or monosub-stituted to tetrasubstituted by amino, N-C1- to C8-alkylamino, N,N-C1- to C8-di-alkylamino, hydroxyl, O-C1- to C8-alkyl-amino and/or C1- to C8-alkoxycarbonyl, and X is =C-N(R4R5) or -C=N-R4, by reacting 2-alkenals of the general formula II
(II), where R1, R2 and R3 have the abovementioned meanings, with primary or secondary amines of the general formula III
( III ), where R4 and R5 have the abovementioned meanings, at from (-20) to 70°C and pressures from 0.01 to 100 bar, by carrying out the reaction without removing the water of reaction and transaminating the product to give the compounds I' and hydrogenating the latter to give novel 1,3-diamines of the general formula IV
(IV),
Description
3 ~
O.Z. 0050/43579 Pre~aration o~ unsaturated amines The present inven~ion relates to a novel procea~
for preparing 1,3 diaminopropene~ by reacting 2-alkenal~
with primary and secondary amines without removing the water of reaction.
Acrolein, Wiley & Sons, N.Y., Chaper 6, (1975) page~ 96 to 109 disclo~es reaction~ o~ primary and secondary aliphatic amines with acrolein to give alkyl-~ub~tituted 1-propens-1,3-diamines. According to thi process, N,N'-dialkyl-l-propene-1,3-diamines are formed ~rom 2 mol of amine with 1 mol of acrolein with removal of water in the pre ence of a dehydrating a~ent or of a water-immi~cible 301vent-US-A-2 565 488 disclose~ ~,N~-dialkyl 1-propene-1,3-diamlne~ and their preparation from 2 alkenals and prLma~y amines under dehydrating ~ondition~ in the pre~ence of dehydrating agent~ ~uch a~ potassium car-bonate.
The addition of di-n-propylamlne to acrolein i9 known from EP-A-424 171. The water of rea~tion must al~o be removed in thi~ proce~s either by usiny a drying agent or alternativ~ly by using a wat~r-immi~cible ~olvent and removing the aqueou~ pha~e.
Th~ proces~e~ known o date ~or preparing alkyl-substituted 1-propene-1,3-diamlne~ ~rom 2-alkenal using primary and econdary aliphati~ amlnes ha~e the di~ad-vantage that they mu~t be carried out with the addition of a dehydrating agent or of a water-immiscible so1vent and removal of an aqueous phase and only modarat~ yield~
are achieved.
: It i~ an object of the pre~e~t invention to remedy tho abovementioned disadvantages.
We have found that this object is aahieved by a novel a~d improved proce~s ~or preparing un~aturated amines o~ the general formula I
' ~ ' ' ' , , ' , ' , , ! ., ' , ' . . ' .' . .
o~o~
O.Z. 0050/43579 Pre~aration o~ unsaturated amines The present inven~ion relates to a novel procea~
for preparing 1,3 diaminopropene~ by reacting 2-alkenal~
with primary and secondary amines without removing the water of reaction.
Acrolein, Wiley & Sons, N.Y., Chaper 6, (1975) page~ 96 to 109 disclo~es reaction~ o~ primary and secondary aliphatic amines with acrolein to give alkyl-~ub~tituted 1-propens-1,3-diamines. According to thi process, N,N'-dialkyl-l-propene-1,3-diamines are formed ~rom 2 mol of amine with 1 mol of acrolein with removal of water in the pre ence of a dehydrating a~ent or of a water-immi~cible 301vent-US-A-2 565 488 disclose~ ~,N~-dialkyl 1-propene-1,3-diamlne~ and their preparation from 2 alkenals and prLma~y amines under dehydrating ~ondition~ in the pre~ence of dehydrating agent~ ~uch a~ potassium car-bonate.
The addition of di-n-propylamlne to acrolein i9 known from EP-A-424 171. The water of rea~tion must al~o be removed in thi~ proce~s either by usiny a drying agent or alternativ~ly by using a wat~r-immi~cible ~olvent and removing the aqueou~ pha~e.
Th~ proces~e~ known o date ~or preparing alkyl-substituted 1-propene-1,3-diamlne~ ~rom 2-alkenal using primary and econdary aliphati~ amlnes ha~e the di~ad-vantage that they mu~t be carried out with the addition of a dehydrating agent or of a water-immiscible so1vent and removal of an aqueous phase and only modarat~ yield~
are achieved.
: It i~ an object of the pre~e~t invention to remedy tho abovementioned disadvantages.
We have found that this object is aahieved by a novel a~d improved proce~s ~or preparing un~aturated amines o~ the general formula I
' ~ ' ' ' , , ' , ' , , ! ., ' , ' . . ' .' . .
o~o~
- 2 - O.Z. 0050/43579 Ri R2 R4 - N ~ x ~I), ¦ R3 where R1,R2,R3,R4,Rs are hydrogen, Cl- to C20 alkyl, C2- to C20-alkenyl, C3- to C9-cycloalkyl, C3- to Ca-cycloalkenyl, phenyl, C7~ to C20-phenylalkyl, C, to C20-alkoxy, phenoxy, C7- to C20-phenoxyalkyl, C~- to C20-alkylamino, phenylamino, C,- to C20-phenylalkylamlno, pyridyl or imidazolyl, or R1 and R2 or R1 and R3 or R2 and R3 toyether are a C2- to Ca-alkylene which is un~ubtituted or monosub~tituted to penta3ubstituted by C~ to C4-alkyl or unsub~tituted or mo~o~ubstituted to tetra~ub~tituted by amino, ~-C,- to C~-alkylamlno, ~,N-C,- to Ca-dialk~lamino, hydroxyl, O-C,- to C~-alkylamino and/or C,- to C8-alkoxycarbonyl, and X is -C-N~RqR5~ or -C=N-R4, by reacti~g 2-alkenaIs of the general formula II
Rl CE30 ~ (II), \
where Rl, R2 ànd R3 have the abovementioned meanings, with ammonia or pximary or ~econdary amines o~ the : g~neral formula III
: R4 : N - B IIII)~
: where R4 and Rs have the aboveM~ntioned meaning~, at from ~(~20) ko 70C and pres~ures from 0.01 ko 100 bar, which compri~e~ carrying out khe reaction without removing the water o~ reaction and kransamlnating the produ~k ko give th- oompound~ I' and hydrogenating the latter to give ; ~
, ~.
.
: , ., , , ~, . ~ .: . , : . ..
2 ~ 0 ~
Rl CE30 ~ (II), \
where Rl, R2 ànd R3 have the abovementioned meanings, with ammonia or pximary or ~econdary amines o~ the : g~neral formula III
: R4 : N - B IIII)~
: where R4 and Rs have the aboveM~ntioned meaning~, at from ~(~20) ko 70C and pres~ures from 0.01 ko 100 bar, which compri~e~ carrying out khe reaction without removing the water o~ reaction and kransamlnating the produ~k ko give th- oompound~ I' and hydrogenating the latter to give ; ~
, ~.
.
: , ., , , ~, . ~ .: . , : . ..
2 ~ 0 ~
- 3 - O. Z . 0050/43579 1, 3-diamine~ and novel 1, 3-diamine~ of the yeneral formula IV
Rl R2 R4--N~ N--R6 (IVj, where Rl R2 R3 R4 Rs R6 R7 ,,,,,, are 5hydrogen~ C1- to C20-alkyl, C2- to C20-alkenyl ~ C3- to C8-cycloallcyl, C3- to C8-cycloalkenyl, phenyl, C7- to C20-phenylalkyl, C~- to C20-alko3~y, phenoxy, C7- t;o C:20-phenoxyalkyl, Cl- to C20-alkylamino, phenylamino, C7- to C20-phenylallylamino, pyridyl or imidazolyl, or and R2 or R1 and R3 or R2 and R3 together are a C2- to Ca-alkylene whit:h i~ unqub~i~uted or mono3ub~tituted ts~
penta~ubqtituted by Cl- to C4~ or un-qub~tituted or mono8ub~tltuted to tetxa~ub~tituted by amino, N~ to C8-alkyl~mino, N,N-Cl- to C8-dialkylamino, hydroxyl, O-C~- to C,~-alkylamino and~or Cl- to C~-alkoxycarbonyl, with the provi~o that R1 and R2 are not hydrogen if R3 is methyl and R~ and Rs, R6 and R7 are in each ca ~ hydrogen or methyl, R4 and R6 are hydrogen and Rs and R7 are eth~ l and al~o R4 and Rs, R6 alld R7 are in each case together (CH2)s or (CH2)2-O~(CH2~2-The process according ~o ~e: in~ention can ~e caxried out a~ $0110w8:
- ~Preparatîon of unsaturated amines I
he 2-alkenal II ~an bs reacted wi~h ammonia or :~ 25 a pr~ary or secondary amine III ei ther batchwi~e or continuou~ly at from (-20) to 70C, preferably 20 to 50C
and :from ~.1 to 10 bar, preferably 1 to 5 bar, partic:ularly preferably atmospheric presx3ure. It may only be neces~ary to u8e preqsures frt)m 2 to 300 bar, :~ 30 preerabl3~ 5 to 200 bar, with gas~ouB amines III. If a primary amine III or III ' is ucied, un~atuxa~ed amine~
or I' ar~ obtained in which X is C=N-R4 or X' i~ C=~-R6.
:
, . , .. , ~ , . . . . .
2 ~
_ 4 _ o.z. 0050/43579 When using a secondary amine III or III', unsaturated amine-~ I or I' are obtained in which X is =C-N(R4Rs) or X' is =C-N-(R ,R ).
The molar ~atio of the prLmary or secondary amine III to the 2-alke~al III should be at lea~t 2 : 1, as a rule from 2 : 1 to 50 : 1, prQferably 2: 1 to 10:
particularly preferably 3 : 1 to 5 : 1.
2-AlkQnals of the general formula II are, for example:
acrolein, methacrolein, crotonaldehyde, 2-methylcroton-aldehyde, 3~methylcrotonaldehyde, 2-ethylacrolein, 2-propylacrolein, 2 isopropylacrolein, 2-nonylacrolein, 2-ethylhe~anal,2-propylheptenal,l-cyclopentenecarboxal-dehyde, l-cyclohexenecarboxaldehyde and cinnamaldehyde.
- Txansamina~ion of the un~aturated amines I
Th~ unsaturated amines I obtained from ammonia or primary or 3econdary amines III with 2-alkenal~ II can ba employed with primary or ~econdary amines III~ to give un~aturated amines I' directly and without removing the water of reaction or excess amine III. However, the un~aturated amine I can also be u~ed as a pure product.
The exchango can be acc31srated and completed by heating the raaction solution to 20 to 150C, pre~erably 30 to 120C, particularly prefsrably 45 to gOC. In this proce0s the nitrogen which i8 next to the double bond i~
preferably 0xchanged. Exchange ~or a primary or secondary amin~ III', who~e boiling point i~ higher than that of the amine of the ~eneral formula I to be removed, i3 particularly preferred. The reaction i~ preferably carried out under a pressure at which the boiling point of ~he amine to be removed i~ from 50 to 80C, iOe. at pre~sures from 0.01 to 3 bar, pre~erably O.OS to 1.5 bar, :~ particularly preferably 0.1 to 0.7 bar.
Ammonia or primary or secondary amine~ III and III' can be employed for preparing un~a~urated amines I
and for preparing un~aturated am~ne3 I' by tran~amination. The most importan~ are li~ted balow:
.
- 5 - O.z. 0050/43579 Ammonia.
Primary amine~ III and III~ are, for examples Primary amine~ without further heteroatoms are, for example: methylamine, ethylamine, n-propylamine, S isopropylamine, n-butylamine, 2-methylpropylamine, tert-butylamine, n-pentylamine, 2-methylbutylamine, 3-methyl-butylamlne, 2,2-dimethylpropylamine, 3,3-dimethylpropyl-amine, n-hexylamine, n-octylamine, 2-ethylhexylamine, tridecylamine, allylamlne, crotylamine, methallylamine, cyclopropylamin~, cyclopentylamlne, cyclohexylamine, be~zylamine and aniline.
Polyfunctionalized amine~ III and III' containing at least one primary amino radical are, for example:
Ethylenediamine, 1,3-propyle~ediamine, 1,4 butylene-diamine, 1,5-pentamethylenediamine, 1,6-hexamethylene-diamin~ ophoronediamine, 2-butyl-2-ethyl-1,5-penta diamine, 1~2-propylenediamine, 2,2-dimet~yl-1,3-propyl-enediamine, ~4,4'-diaminodicyclohexylmethane, 3,3'-di-methyl-4,4'diaminodicyclohexylmethane, 4,4'-diaminodi-phenylmethane, N-methylethyle~ediamine, N,N-dimethyl-ethylenediamine, N,N-diethylethylenediamine, N-methyl-1,3-propylenediamine, N,N-dLmethyl-1,3-propylenediamin~, N,N-diethyl-1,3-propylenediamine, N-cy~lohexyl-1,3-propylenediamine~ 1-diethylamino-4-aminopentane, diethylenetriamine, N,N-dLmethylethylenetriamine, dimethylpropylenetriamin~, N-(2-amino~thyl)-1,3-propanediamine, N,N'-bi~(3-aminopropyl)-ethylenediamine a~d ~ dimethyl-1,6-hexamethylenediamine.
Primary amine~ III and III' containing further : 30 heteroatom ~ubstituents are, ~or example:
2-Aminoethanol, 1-amino-2-propanol, 2-(2-amlnoethoxy)-: ethanol, 3-aminopropanol, 2-amino-1-butanol, 4,9-dioxado-decan 1,12-diamine, 4,7,10-trioxatridecan-1,13-diamine, 2-methoxyethylamine,2-ethoxyethylamine,3-meth3xypropyl-amlne,3-ethoxypropylamlne,3-~2-ethylhexoxy)propylamine, 3-(2-methoxyethoxy)propylamine, 2-methoxyphenylethyl-amlne, 4-methoxyphenylethyl d ne and homoveratrylamine.
- 6 - O.Z. 0050/43579 Secondary amines III and III' are, for example:
Secondary amines without ~urther heteroatoms are, for example: dLmethylamine, diethylamine, di-n~propylamine, di-isopropylamine, di-n-butylamine, di-(2-methylpropyl)-S amine, di-tert-butylamine, di-n-pentylamine, di-(2-methylbutyl)amin~, di-(3-methylbutyl)amine, di-(2,2-dLmethylpropyl)amine, di-(3,3 dimethylpropyl)amine, di-n-hexylamine, di-2-ethylhexylamine, di-tridecylamine, N-methylbutylamine, N-ethylbutylamine, diallylamine, dicrotylamine, dLmethallylamine, dicyclopropylamine, dicyclopentylamine, ~-methylcyclohexylamine, N-ethyl-cyclohexylamine, dicyclohe~ylamine, N-methylaniline, N-ethylaniline and diphenylamine.
Secondary amine~ III and I}I' containing further heteroa~om sub~tituent~ ar~, for example:
Diethanolamina, di-isopropanolamine, methylethanolamine, ethylethanolamine, butylethanolamine, cyclohe~yl-ethanolamine, hydroxyothylaniline and di-2-methoxyethyl-amine.
- Hydrogenation of unsaturated amine~ :
~he unsaturated amine~ I obtained from reacting - -ammonia or primary or ~econdary amine~ III and 2-alkenal~
II can be hydrogenated on customsry hydrogenation catalysts æuch as palladium, platinum, ruthenium, 2~ rhodium, cobalt, nickel and copper as a metal or metal mixtura or o~ a support material such a~ alumina,-silica, activ~ carbon, zirconium o~ide or titanium dioxide, in particular on palladium as metal or on a support material ~uch a3 alumina, silica or ac~ive carbon, without working up and in the presence of the water of reaction, preferably without working up and without remoYing ~he water o~ reactionp to give tho corre~pond~ng ~aturated 1,3-diami~e~ IV. The u~saturated amine~ I' prepared by amine exchange reaction can equally be hydrogenated, pre~erably withou~ working up ~he crude : produc~. -The hydrogenation can be carried out in the ,.
_ 7 _ O.Z. 0050/43579 pre~ence or ab ence of inert ~olvent~ such as ether~, for example methyl tert~butyl ether, tetrahydrofuran and dioxane~ or esters, for example methyl acetate and ethyl acetate, at from 0 to 150C, preferably 10 to 80C, particularly preferably 30 to ~0C. The hydrogen pre~ure is from 1 to 350 bar, preferably from 1 to 100 bar.
The ~ub~tituent~ Rl, R2, R3, R~, Rg, R6 and R7 in the compounds of the general formulae I, I~, II, III, III' and IV have the following meanings:
n 1 ~2 R3 R4 Rs R6 R7 e R ,~ , , , , , ar - hydrogen, - Cl- to C20-alkyl, preferably Cl- to Cl2-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, i~obutyl, sec-bu~yl, tert-kutyl, n-pentyl, isopentyl, sec-pentyl, neo-penty~, 1,2-dimethylpropyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl and i~ododecyl particularly prefsrably Cl- to C~-alkyl such as methyl, ethyl, n-propyl, i opropyl, n-butyl, isobutyl, sac-butyl and tert-butyl, - C2- to C20-alkenyl, preferably C2- to Cl2-alkenyl such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, ~ec-butenyl, tert-but2nyl, n-pen~enyl, isopenten~l, sec-pentenyl, neo-pentenyl, 1,2-dimethenylpropenyl, n-hexenyl, isnhexenyl, sec-hexenyl, n-heptenyl, isoheptenyl, n-octenyl, i~ooctenyl, n-nonenyl, isononenyl, n-decsnyl, isodecenyl, n-undecenyl, isoundecen~l, n-dodecenyl and isodcdecanyl, particularly preferabl~ C~- to C4-alkenyl ~uch as e~henyl, n-propenyl, : 30 isopropenyl, n-butenyl, i obutanyl, sec-butenyl and ter~-butenyl, : - C3- to C8-cycloalkyl such a~ cyclopropyl, cyclobutyl, cy¢lopentyl, cyclohexyl, cycloheptyl and cyclooctyl, :
preferably cyclopentyl, cyclohexyl and cyclooctyl, particularly preferably cyclopentyl and cyclohe~yl, - C3- to C8-cyeloalkenyl i~iuch as cyelopropenyl, cyclo-butenyl, cyelopentenyl, cyclohexenyl, cyclohept~nyl and , ' :', ,: ': ', '' ' ' ' ' ' '.' ;' ' ' , : ' ' , ' ~.:, ' ' ' '. '': , ~' :', - ' ' " '' ', .' ";' ' ' . ' ' '' ' "" '. ' . ' ~ ': '' ' : ' ' , ' ' , . ' :' ~ ' , ', : . : ' ' , . i' , , ' . " . " : ' ',, , . ~' .' ', ' , ~' " ~ ,,'' ' '' , " ' ' ' ' ' ' ' 2 ~
- 8 - O.z. 0050/~3579 cyclooctentyl, preferably cyclopentenyl, cyclohexenyl and cyclooctenyl, - phenyl, - C7- to C20-phenylalkyl~ preferably C7- to C~2-phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2 phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl, 1-phenethyl and 2-phenethyl, - C1- to C20 alkoxy, preferably C,- to C12-alkoxy ~uch a~
methoxy, ethoxy, n-propoxy, i opropoxy, n-butoxy, i~obutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, neo-pentoxy, 1,2 dimethyl-propoxy, n-hexoxy, isohexoxy, cec-he~oxy, n heptoxy, i~oheptoxy, n-octoxy, i900CtoXy~ n-nonoxy, isononoxy~ n-decoxy, isodecoxy, n-undecoxy, i~oundecoxy, n-dodecoxy and isododecoxy, particularly preferably C1- to ~4-alkoxy such as methoxy, ethoxy, n-propoxy, isopropcxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy~
- phenoxy, - C7- to C20-phenoxyalkyl, preferably C7- to C12-phenoxyalkyl such as benzoxy, l-phenoxyethyl, 2-phenoxyethyl, 1-phenoxypxopyl, 2-phenoxypropyl, 3-phenoxypropyl, 1-phenoxybutyl, 2-phenoxybutyl, 3 phenoxybutyl and 4-phenoxybutyl, particularly preferably benzoxy, 1 phenoxysthyl and 2-phenoxy~thyl, - C~- to C20-alkylamirlo, preferably Cl- to Cl2-alkylamino such a~ methylamino, ethylamlno, n-propylamino, i~opropylamlno, n-butylamino, isobutylamino, sec-butqlamino, ter~-butylsmino, n-pentylamino, isopentylamino, sec pentylamino, n~o pentylamino, 1,2-dimethylpropylamino, n-hexylamino, i~ohexylamino, sec-hexylamino, n-heptylamino, isoheptylamino, n-octylamino~ isooctylamino, n-nonylamino~ isononylamino, n-decylamino, isodecylamino, n-undecylamino, isoundecylæmino, n-dodecylamlno and i~ododecylamino, particularly preferably Cl- to C4-alkylamino such a~
- , . ,.. , ., . , ~ . . , . , .. ,: : : , : ; ; ;
-` 2~1Q~
_ g _ o.z. 0050/43579 methylamino, ethylamino, n-propylamino t isopropylamino, n-butylamino, isobutylamino, sec-butylamino and tert-butylamino, - phenylamino, - C7- to CzO-phenylalkylamino, preferably C7- to Cl2-phenylalkylamino ~uch as benzylamino, l-phen ethylamino, 2-phenethylamino, l-phenylpropylamino, 2-phenylpropylamino, 3-phenylpropylamino, l-phenyl-butylamino, 2-phenylbutylamino, 3-phenylbutylamino and 4-phenylbutylamino, particularly preferably benzylamino, 1-phenethylamino and 2-phenethylamino, - pyridyl, - imidazolyl or R~ and R2 or Rl and R3 or R2 and R3 together are a C2- to C8-alkylene which ~ 8 unsub~tituted or mono- to pentasubstituted by Cl- to C4-alkyl or un ub~ti~uted or mono~ub~tituted to tetra~ub~tituted by amino, N-Cl- to C3-alkylamino, N,N-Cl- to C~-dialkylamino, hydroxyl, O-C1- to C~-alkylamino and/or Cl- to C8-alkoxycarbonyl, such as aminoalkyl, N-methyl-aminoalk~ ,N-dLmethylamino-alkyl, N-ethylaminoalkyl, N,N-diethylaminoalkyl, methoxyal~yl and ethoxyalkyl, preferably aminoethyl, N-methylaminoethyl, N,N-dimethylaminoethyl, aminopropyl, N-methylaminopropyl, N,N~dimethylaminopropyl, h~dro~yethyl, methoxyethyl, ethoxyethyl, hydroxypropyl, methoxypropyl and ethoxypropyl.
~ he ~ollowing may be men~ioned a~ novel 1,3-diamines IV-N,N~-2-trima~hyl 1,3-propanediamine, N,N,~,N~-~etra-ethyl-2 methyl-1,3-propanediamine, N,~-di-n-propyl-2-methyl-1,3-propanediamine, N t N,N~,N~-tetra-n-propyl-2-methyl-1,3-propanediamine, N,N'-di-i-propyl-2-methyl-1,3-propanediamine, N,N'-di-n-butyl-2-me~hyl-1/3-propane-diamine, N,N,N~,N'-tetra-n-butyl-2-methyl-1,3-propane~
diamine, N,N'-dicyclohexyl-2-methyl-1,3-propanediamin0, N,N'-di~2-ethylhaxyl)-2-methyl-1,3-propanediamine, N,N,~'/N'-tetra(2-ethylhexyl)-2-methyl-1,3-propanedi-....... . . .
.. ! , " . , ' . , ~ : " . ~ , .. , ., . ,~
- 10 - O.Z. 0050/43579 amine, N,N~-di(2-hydroxyethyl) 2-methyl-1,3-propanedi-amine, N,N'-di(3 hydroxypropyl)-2-methyl-1,3-propanedi ~
amine, N,N'-di(3-methoxypropyl)-2-methyl-1,3-propanedi-amine, N,N'-di(N,N-dimethyl-2-aminoethyl)-2-methyl 1,3-propanediamine, N,N'-di(N,N-dimethyl-3-am~nopropyl)-2~methyl-1,3-propanediamine, N,N'-diphenyl -2-methylo 1,3-propanediamine, N,N~-dibenzyl-2-methyl-1,3-propane-diamine, di(N-i-propylamino-2-methylpropyl)-1,6-hexarldi-arnLne, N-cyclohexyl-N'-i-propyl-2-methylpropane-1,3-diamine, N,N~-di-n-propyl-N'-i-propyl-2-methylpropane-1,3-diam~ne, N-i-pxopyl-N'-phenyl-2-methylpropane-1,3-diamine, propyl-N~-(2-hydroxyethyl)-2-methylpropane-1,3-diamine, N-i-propyl-N '-(3-hydroxypropyl)-2-methylpropane-1, 3-diamine, N-i-propyl-N' (3 mathoxypropyl)-2-methyl-propane-1,3-diamine, N-i-propyl-N'-(3-methylam~nopropyl)-2-methylpropane-1,3-diamine, N-i-propyl~ 3-dimethyl-am~nopropyl)-2-methylpropane-1,3-diam~ne, 11,14-dimethyl-1,5,9,13-tetraazapentadecan, 1-cyclohexylamino-2-methyl-3 piperidylpropane, 2-methyl-1-piperidyl 3-i-propylamino-propane, 2-methyl-1-morpholino-3-i-propylaminopropane, 2-methyl- 1-morpholino-3-piperidylpropane, 2,5,12,15-tetramethyl-3,7,10,14 tetraazahexadecan, 2,5,16, 19-tetramethyl-3,7, 14y 18-tetraa~aeicosan, 2,5,17,20-tetramethyl-3,7,11,15,19-pentaazaheneicosan, N,~'-di-t-butyl-l,3-propanediamine, ~,N'-di-t-butyl-2-ethyl-1,3-propanediamine, N,~ di-t-butyl-2-n-nonyl-1,3-propanediamine, N,N'~di-i-propyl~l,3-butanediamine, M,N'-di-n-butyl-1,3-butanediamirle, N,N '-di-n-butyl-2-n-propyl-1,3-pentanedia~Line, 1~,N'-di-i-propyl-1,3-butanedi-am~ne.
N,N' -alkyl-~ub tituted 1,3-propanediamine~ are u~ed, for example, in the preparation of CFC-free polymer~, ae catalyst~ for polyurethanes and curing ;~gen~s, e.g~ for epoxy resin3, a~ components or additive~ in the prepara-tion o c:ertain types o~ nylon, as ~tarting materials for polyurea~ or in the preparation of iEinishing agents for 2'~
- 11 - o.z. oOsO/43579 textile fibers and for adhesives.
EXAMPLES
- Preparation of unsaturated amine~ I and subsequent hydrogena~ion 26.3 g (0.375 mol) of methacrolein were added dropwise over an hour to 88.5 g (1.5 mol) of isopropylamine such that the temperature does not rise above 35C. qlhe mixture i~ stirred at 40C for an hour and the crude isopropylaminQ~methacrol~in condansation product is hydrogenated over 3 g of palladium on active carbon ~10% Pd) at 50C and 100 bar of hydrogen until ab~orption of hydrosen i~ complete. Fractional di ~illation (b.p.- 100C/25 mbar) yielded 52 g ~81 %3 of N,~'-dii~opropyl-2-methyl 1,3-propanediamine.
26.3 g (0.375 mol) of methacrolein were added dropwise over an hour to 88.5 g (1.5 mol) of isopropylamine such that the temperature doe~ not rise above 45~C. The mixture i~ ~tirre~ at 40C for an hour and the crude isopropylamine!methacrolein condensation product i8 hydrogenated over 0.5 g o~ palladium on active carbon (10 % Pd) at 50C and a hydrogen pre~surs of 100 bar until absorption of hydrogen i~ complete. Fractional distillation (b.p.: 100C/25 mbar) yialded 52 g (81 ~) of N,N~-diisopropyl-2-methyl-1~3-propanediamine.
EXA~P~ 3 61.3 g (0.875 mol3 of methacrolein were added dropwi~e over an hour ~o 2Q6.5 g (3.5 mol~ of isopropylamine ~uch ~hat the ~mperature does not ri~e above 35C. The mixture is stirred at 40C for an hour and the crude isopropylamine/methacrolein condena~ion product i~ hydrogenated over 5 g of palladium on active : carbon (10~ Pd) at 25C an~ atmo3pheric pre~ure until ah80rption of hy~ro~en i~ complete. ~ractional distillation (b.p.: 98C/20 ~bar) yieldad 118 g (79%) of N,N'-diisopropyl-2-mothyl-1,3-propanediami~e.
.
. : . , . .. : . , 21~ j~OO
- 12 - O. Z . ~050/43579 EXA~LE 4 105 ~ (1.5 mol) o~ methacrolein were added dropwise over an hour to 3.54 g (~ mol) of isopropylamine such that the temperature does not ri~e above 45C. The mixture is 3tirred at 40C for an hour and thP crude i~opropylamine/methacrolein condensation product i~
hydrogenated, after diluting with 400 ml of tetrahydxofuran, over 15 g of palladium on active carbon (10 ~ Pd) at 50C and 100 bar of hydrogen until absorp-t~on of hydrogen is complete. Fractional distillation(b.p.: 98C/20 mbar) yielded 212 g ~83%) of N,N'-diiso-propyl-2-methyl-1,3-propanediamine.
EXANPLE ~
By a method 3imilar to Example l, 310 g (83 %) of N,N~-di-n-bu~yl-2-m~thyl-1,3-propanedia~ine (b.p.:
97C/1 mbar) were obtained from 140 g (2 mol) of methacrolein and 672 g (8 mol) of n-bu~ylamine (molar ratio 1 : 4) ovar 15 g of palladium on active carbon (10%
Pd)- . .
By a mathod similar to Example 4, 346 g (87 %) of N,~'-di-tert-butyl-2-methyl-1,3-propanediamine (m.p.:
58C; b.p.s 106C/lS mbar) were obtained from 140 ~ (2 mol) o~ methacrolein and 504 g (6 mol) o~ tert-butylamine (molar ratio 1 : 3) over lS g of palladium on active carbon (10 % Pd~.
. EXA~PL~ 7 B~ a method ~imilar to Example 1, 459 g (83 %) of N,N'-dicyclohexyl-2-methyl-1,3-propanediamine (b.p.: 150 to 160~C/1 mbar) were obtained fro~ 153.5 g (2.2 mol~ of met~acrolein and 870 g (8.8 mol) o~ cyclohe~ylamine (molar ratio 1 : 4 ) over 15 g of palladium on active carbon (10 ~ Pd~.
By a method ~imilar to Example 1~ 398 g (87 ~) of N,N'-di-t2~ethylhexyl)-2-methyl-1,3-propanediamine (b.p.: 170C/1 mbar) were obtained from 100 g (1.5 mol) :, ... ,:: , , .. , :, :: . . . . .......................... .. . - .~:
., .. . , ,. .................. ,, ,,.. .. . . : ... : ., : : . . . . . - . . .. . , . , ., , ~ . ,.. . : . , : .. .: . .. ..
` - 13 - O.z. OOS0/43579 of me~hacrolein and 754 g (5.8 mol) of 2-ethylhexylamine (molar ratio 4 : 1) over 15 g of palladium on active carbon (10 ~ Pd).
E~AMPLE 9 By a method ~ ~ilar to Example 1, 76 g (20 %) of N,N'-dibenzyl-2~methyl-1,3 propanediamine (b.p.: 59C/1 mbar) were obtained from 112 g (1.6 mol) of methacrolein and 686 g (6.4 mol) of benzylamine (molar ratio 4 : 1) over 10 g of palladium on astive carbon (10 ~ Pd).
By a method ~imilar to Example 1, 376 g (73 %) of N,N'-di-(N,N-dimethyl-3~aminopropyl)-2-methyl-1,3-propanediamine ~b.p.: 159C/5 ~bar) were obtained from 140 g (2 mol) of methacrolein and 816 g (8 mol) of N!N-dimethylprop~lenediamin2 (molar ratio 4 : 1) over 15 g o~
palladium on active carbon (10 % Pd~.
EXA~PLE 11 By a method ~imilar to Ex~mple 1, 167 g (64 ~) of N,N'-di-(2-aminoethyl~-2-methyl-1~3-diaminopropane (b.p.: 118 to 130Ctl mbar) were obtained from 102 g (1.5 mol) of methacr~lein and 901.5 g (15 mol) of ethyl-enediamine (molar ratio 1 : 10~ over 15 g of palladium on active carbon (10 ~ Pd).
By a m~thod ~imilar to Ex~mple 1, 310 g (59 %) of N,N'-di-(2~hydroxyethylj-2-methyl-1,3-propanadiamine (b.p.: 162 to 172C/1 mbar).were obta~ned from 140 g (3 mol) of methacrolein and 488 g (8 mol3 o~ ethanolamine (molar ratio 1 : 4) over 15 g of palladium on active 3Q carbon (10 % Pdj.
.' ~XANPL~ 13 By a method similar to Example 1, 350 g (69 %) of N,~'-di (2-methoxyethyl)-2~methyl 1,3-propaned~amine (b.p.~ 96C/1 mbar) were obtained from 17S g (2.5 mol) of methacrolein and 750 q (10 mol) of me~hoxyethylamine (molar ratio 1 : 4) over 15 g of palladium on active - ,, ~ , :,, - -. , .,: ,. . . . ..
, , ,:::, ~. . . . . . .
~1~5~
- 14 - O.Z. 0050/43579 carbon (10 % Pd).
By a method sLmilar to Example 1, 150 g (60 %) of N,N'-dii~opropyl-1,3~butanediamine (b.p.: 43C) were 5obtained from 102 g (1.5 mol) of crotonaldehyde and 344 g (5.8 mol) of isopropylamine (molar ratio 1 : 4) over 10 g of palladium on active carbon (10 ~ Pd).
By a method ~imilar to Example 1, 162 g (81 ~) of 10N,N'-di-n-butyl-1,3-butanediamine (b.p.: 120C/18 mbar) were obtained from 70 g (1 mol3 of crotonaldehyde and 584 g (8 mol) of N-butylamine (molar ratio 1 : 8) over 15 g of palladium on active carbon (10 ~ Pd).
15By a method ~Lmilar to ExEmple l, 440 g (67 %) of N,N'-di-tert-~u~yl-2-nonyl-1,3-propanediami~e (b.p.: 150C/1 mbar) w~r~ obta$ned from 546 g (2.1 mol3 of 2-nonylacrolein (a~ a 70 % strength ~olu~ion in decane) a~d 444 g (6 mol~ of tert-butylamine ~molar ratio 201 : 3) over 15 g of palladium on active carbon (10 % Pd).
EXAMPL~ 17 By a method similar to Example 1, 395 g (84 %) of N,N'~di-tert-butyl-1,3-propanediamine (b.p. 5 132C/
100 mbar) ware obtained from 140 g (2.5 mol) of acrolein 25and 732 g (10 mol) of tert-butylamine (molar ratio 1 : 4) over I5 g of palladium on active carbon (10 ~ Pd).
. E~AMPL~ 18 : ~By a~method ~imilar to ~ample 1, 29 g ~80 ~) of 1,3-dipiperidyl-2-methylpropane (b.p.: 90 ~o 30: 100C/l mbar) were obtained from 10 g (0.14 mol) of mathacrolein and 50 g (0.6 mol) of piperidine (molar :~ ratio 1 s 4.2) over 2 g of Pd on active carbon (10 % Pd3.
EXANP~ I9 By a method ~imilar to Example 1, 250 g (40 %) of 35N~N~N',N'-tetra-n-butyl-2-methyl-1,3-propa~ediamine (~.p.: 125C/1 mbar) were obtained from 140 g (2 mol) of methacrolein and 155 g (12 mol) o~ di n-butylamine (molar '' ~
' " ,.
- 15 - O.~. 0050/43579 ratio 1 : 6) over 15 g of Pd on active carbon (10 % Pd).
By a method similar ~o Example 1, 149 g (50 %) of N,N,N',N'-tetra-n-propyl-1,3-propanediamine (b.p.: 137C~
5were obtained from 68 g (1.2 mol) of acrolein and 740 g (7.3 mol) o~ di-n-propylamine (molar ratio 1 : 6) ovar 15 g of Pd on active carbon (10 % Pd).
COMP MISON EXAMPLE
According to J. Am. Chem. Soc. 74, tl952) 2016 to 102018 Table 1, 10th example 35 g (0.5 mol) of methacrolein were added dropwise over an hour to a solution of 25 g of anhydrou~
pota~sium carbonate in 147.5 g (2.5 mol) of isopropylamine and from 5 to 10QC.-After filtering off 15the pota~sium carbonate, the crude isopropylamine/-methacrolein conden~ation product wa~ hydroge~ated over 5 g of Raney ~ickel freed from water at 105C and 70 bar of hydrogen over 6 h. Fractional distillation (b.p.: 80-100C/35 mbar) yielded 47 g ~50 ~i) of N,~'-diisopropyl-2-2~methyl-1,3-diamlne. The literature yield is 58 %.
Examples of the continuoue hydrogenation of the Schiff ~ 9 base~:
EXAMPL~ 21 A vertically arranged tubular reactor ~diameter:
2514 mm, packing height: 50 cm, oil-heated double jaak~t) wa~ packed with 75 ml (47.6 g~ of a catalyst containing O.5 % Pd on y-alumina in the form of 4 mm strands (preparation of cataly~t by pora LmmersiOn of yoalumina using aqueou~ palladium nitrate ~olution and drying at 30120~C). The catalyst i9 reduced ln situ.
20 g of a ~olution of 155 g (2.6 mol) of iscpropylamine and 61 g (0.88 mol) of methacrolein in -200 g of t~trahydrofuran are pa~ed through the reactor hourly from the bottom upward~. 10 (s~t~pO) of hydrogen 35are pa~sed through th~ reactor hourly at a pre~ure of 80 bar. The temperature i8 70C. The: di~charged reactio~
produat i8 decompreY~ed to atmospheric pre3sur~. The .
, - 16 - O.Z. 0050/43579 yield of N,N' diisopropyl-2-methyl-1,3-diaminipropane i~
80 %.
EXAMP~E 22 N,N,N',N',2-pentamethyl-1,3-diamlnopropane A vertically arranged tu~ular reactor (diameter:
14 mm, packing height: 50 cm, oil-heated double jacket) wa~ packed with 75 ml (47.6 g) of a cataly~t containing O.5 ~ Pd on y-alumina in the form of 4 mm ~trands (preparation of catalyst by pore imm~r~ion of ~-alumina . using aqueous palladium nitrate ~olution and drying at 120C). The cat~ly~t i~ reduced in ~itu.
lOQ ml of a 20% strength ~olution of methacrolein in tetrahydro~uran and 60 ml of dimethylamine are pa~ ed through the reactor hourly from the bottom upward~. 10 (~.t.p.) of hydrogen are pa~ed through the reactor hourly at a pre ~ur~ of 75 bar. The temperature is 70C.
The discharged reaction product is decompressed to atmo~pheric pressure, fr2ed from dL~ethylamlne and distiIled. Tha di~charged reaction product collected over the course of an hour yield~, after distillation at 70C/100 mbar, 28 g of N,N,N~ 2-pe~tamethyl-1,3-diaminopropane. Ths yield iB 85 96.
- Transam~nation of the unsaturated amines I and ubsequent hydrogenation EXA~hl~ 23 168 g t 2, 4 mol ) of methacrolein were added dropwi~e in th~ course of an hour to 354 g l6 mol3 of i~opropylamine uch that the temperature doe~ not exc:eed 35C~ Ths mixtur~ i~ stirred at 40C for an hour. This crude i~opropylamine/methacrol~i~ conden~ation product i~
treated at 40C with 287 g (2.9 mol) of cyclohexylamine and i~opropylamlne i~ sLmultaneou~ly di~tilled o~f. The un~ymmetrically ~ubst~tuted diamine precursor thus o~tained i~ diluted with 400 ml o~ tetrahydrofuran and hydrogenated over 15 g of Pd on active carbon (10 % Pdj at 50C and 100 bar until absorption o~ hydro~en i~
completo. Practional di tillation (b-p-. 99 to , .
. : , -,, ~
. ~
- 17 - O.Z. OOS0/43579 106C/1 mbar) yielded 311 g (73 ~) of N-iRopropyl-N'-cyclohexyl-2-methyl-1,3-propanediamine.
EX~MPLE 24 By a method ~imilar to Example 23, 191 g (52 %) of 11,14-dimethyl-1,5,9,13-tetrsa2apentadecan (b.p.: 188 to l90~C/5 mbar) were obtained from 105 g (1.5 mol) of methacrolein, 267 g (4.5 mol) of isopropylamine and 196.5 g (1.5 mol) of dipropylenetriamine (molar ratio 1 : 3 : 3) over 15 g of active carbon (10 % Pd) and in 400 ml of tetrahydrofuran.
~XAMPLE 25 By a method similar to Example 23, S3 g (52 %) of dl~ isopropylamino-2-methylpropyl)-1,6 hexanediamine (~.p.s 170C/1 mbar) wsre obtained from 50 g (Q.71 mol) of methacrolein, 176 g ~2098 mol) of isopropylaminQ and 41.5 g (0.35 mol) o~ hexamethylsnediamine (molar ratio 2 : 8 : 1) over 5 g of palladium on active carbon (10 % Pd) and in 50 ml of tetrahydrofuran.
By a method sLmilar to Ex2mpla 23, 171 g (51 %) of N-isopropyl-N'-(N-methyl-3-aminopropyl)-2-methyl-1,3-propanediamine (B.P.: 90 to 96C/l mbar) were obtained from 116 g (1.7 mol) of methacrolein~ 245 g (4.2 mol) of isopropylamine and 176 g (2 mol) of N-methylpropylenedi-amino (molar ratio 1 : 2.5 ~ ) over 10 g of palladium on acti~e carbon (10 ~ Pd ) a~ in 40Q ml of tetrahydro-furan.
: EXANPLE 27 By a method similar to exampl~ 23, 61 g (47 %) o~
1-i~opropylamino-2-me~hyl-3-morpholinspropane (b.p.s 75~C) wers obtained from 61.3 g (0.78 mol) o methacrolein, 206 g (3.5 mol) of i~opropylamine and 76 g (0.8~ mol) of morpholin~ (mol~r ratio 1 : 4 ~ 1) over 10 g of palladium on active carbon (10 ~ Pd).
3S E~ 28 By amethodsimilar to E~cample 23, 56 g (50 %) of l-cyclohexylamino-2-methyl-3-piperidylpropane , ' :. ' ' . ' ' ' . . .'. ' .
- c2~J ~
`18 - O.Z. 0050/43579 (b.p.. 120C/1 mbar) were obtained from 35 g (0.5 mol) o me~hacrolein, 170 g (2 mol) of piperidine and 43.5 g (0.5 mol~ of cyclohexylamine (molar ratio 1 : 4 : 1) over 3 g of Pd on active carbon (10 ~ Pd) and in 50 ml of S tetrahydrofuran.
By a method ~imilar t~ Example 23, 17 g (16 %) of l-morpholino-2-methyl-3-piperidylpropane (b.p.~ 110C/
1 mbar) were obtained from 35 g (0.5 mol) of 10methacrolein, 170 g (2 mol) of piperidine and 43.5 g (O.S mol) of morpholine (molar ratio 1 : 4 : 1~ over 3 g of Pd on ac~ive carbon (10 % Pd).
' , ' .. ... .
- , ., . . ., , . . ~..... .. ", . , : . , . .. ; . ...
.. ,: ., . . ~. . , .. . . . : , . . ,, :. ~, :.. 1 ., .. , . , . .,; . , .. :
Rl R2 R4--N~ N--R6 (IVj, where Rl R2 R3 R4 Rs R6 R7 ,,,,,, are 5hydrogen~ C1- to C20-alkyl, C2- to C20-alkenyl ~ C3- to C8-cycloallcyl, C3- to C8-cycloalkenyl, phenyl, C7- to C20-phenylalkyl, C~- to C20-alko3~y, phenoxy, C7- t;o C:20-phenoxyalkyl, Cl- to C20-alkylamino, phenylamino, C7- to C20-phenylallylamino, pyridyl or imidazolyl, or and R2 or R1 and R3 or R2 and R3 together are a C2- to Ca-alkylene whit:h i~ unqub~i~uted or mono3ub~tituted ts~
penta~ubqtituted by Cl- to C4~ or un-qub~tituted or mono8ub~tltuted to tetxa~ub~tituted by amino, N~ to C8-alkyl~mino, N,N-Cl- to C8-dialkylamino, hydroxyl, O-C~- to C,~-alkylamino and~or Cl- to C~-alkoxycarbonyl, with the provi~o that R1 and R2 are not hydrogen if R3 is methyl and R~ and Rs, R6 and R7 are in each ca ~ hydrogen or methyl, R4 and R6 are hydrogen and Rs and R7 are eth~ l and al~o R4 and Rs, R6 alld R7 are in each case together (CH2)s or (CH2)2-O~(CH2~2-The process according ~o ~e: in~ention can ~e caxried out a~ $0110w8:
- ~Preparatîon of unsaturated amines I
he 2-alkenal II ~an bs reacted wi~h ammonia or :~ 25 a pr~ary or secondary amine III ei ther batchwi~e or continuou~ly at from (-20) to 70C, preferably 20 to 50C
and :from ~.1 to 10 bar, preferably 1 to 5 bar, partic:ularly preferably atmospheric presx3ure. It may only be neces~ary to u8e preqsures frt)m 2 to 300 bar, :~ 30 preerabl3~ 5 to 200 bar, with gas~ouB amines III. If a primary amine III or III ' is ucied, un~atuxa~ed amine~
or I' ar~ obtained in which X is C=N-R4 or X' i~ C=~-R6.
:
, . , .. , ~ , . . . . .
2 ~
_ 4 _ o.z. 0050/43579 When using a secondary amine III or III', unsaturated amine-~ I or I' are obtained in which X is =C-N(R4Rs) or X' is =C-N-(R ,R ).
The molar ~atio of the prLmary or secondary amine III to the 2-alke~al III should be at lea~t 2 : 1, as a rule from 2 : 1 to 50 : 1, prQferably 2: 1 to 10:
particularly preferably 3 : 1 to 5 : 1.
2-AlkQnals of the general formula II are, for example:
acrolein, methacrolein, crotonaldehyde, 2-methylcroton-aldehyde, 3~methylcrotonaldehyde, 2-ethylacrolein, 2-propylacrolein, 2 isopropylacrolein, 2-nonylacrolein, 2-ethylhe~anal,2-propylheptenal,l-cyclopentenecarboxal-dehyde, l-cyclohexenecarboxaldehyde and cinnamaldehyde.
- Txansamina~ion of the un~aturated amines I
Th~ unsaturated amines I obtained from ammonia or primary or 3econdary amines III with 2-alkenal~ II can ba employed with primary or ~econdary amines III~ to give un~aturated amines I' directly and without removing the water of reaction or excess amine III. However, the un~aturated amine I can also be u~ed as a pure product.
The exchango can be acc31srated and completed by heating the raaction solution to 20 to 150C, pre~erably 30 to 120C, particularly prefsrably 45 to gOC. In this proce0s the nitrogen which i8 next to the double bond i~
preferably 0xchanged. Exchange ~or a primary or secondary amin~ III', who~e boiling point i~ higher than that of the amine of the ~eneral formula I to be removed, i3 particularly preferred. The reaction i~ preferably carried out under a pressure at which the boiling point of ~he amine to be removed i~ from 50 to 80C, iOe. at pre~sures from 0.01 to 3 bar, pre~erably O.OS to 1.5 bar, :~ particularly preferably 0.1 to 0.7 bar.
Ammonia or primary or secondary amine~ III and III' can be employed for preparing un~a~urated amines I
and for preparing un~aturated am~ne3 I' by tran~amination. The most importan~ are li~ted balow:
.
- 5 - O.z. 0050/43579 Ammonia.
Primary amine~ III and III~ are, for examples Primary amine~ without further heteroatoms are, for example: methylamine, ethylamine, n-propylamine, S isopropylamine, n-butylamine, 2-methylpropylamine, tert-butylamine, n-pentylamine, 2-methylbutylamine, 3-methyl-butylamlne, 2,2-dimethylpropylamine, 3,3-dimethylpropyl-amine, n-hexylamine, n-octylamine, 2-ethylhexylamine, tridecylamine, allylamlne, crotylamine, methallylamine, cyclopropylamin~, cyclopentylamlne, cyclohexylamine, be~zylamine and aniline.
Polyfunctionalized amine~ III and III' containing at least one primary amino radical are, for example:
Ethylenediamine, 1,3-propyle~ediamine, 1,4 butylene-diamine, 1,5-pentamethylenediamine, 1,6-hexamethylene-diamin~ ophoronediamine, 2-butyl-2-ethyl-1,5-penta diamine, 1~2-propylenediamine, 2,2-dimet~yl-1,3-propyl-enediamine, ~4,4'-diaminodicyclohexylmethane, 3,3'-di-methyl-4,4'diaminodicyclohexylmethane, 4,4'-diaminodi-phenylmethane, N-methylethyle~ediamine, N,N-dimethyl-ethylenediamine, N,N-diethylethylenediamine, N-methyl-1,3-propylenediamine, N,N-dLmethyl-1,3-propylenediamin~, N,N-diethyl-1,3-propylenediamine, N-cy~lohexyl-1,3-propylenediamine~ 1-diethylamino-4-aminopentane, diethylenetriamine, N,N-dLmethylethylenetriamine, dimethylpropylenetriamin~, N-(2-amino~thyl)-1,3-propanediamine, N,N'-bi~(3-aminopropyl)-ethylenediamine a~d ~ dimethyl-1,6-hexamethylenediamine.
Primary amine~ III and III' containing further : 30 heteroatom ~ubstituents are, ~or example:
2-Aminoethanol, 1-amino-2-propanol, 2-(2-amlnoethoxy)-: ethanol, 3-aminopropanol, 2-amino-1-butanol, 4,9-dioxado-decan 1,12-diamine, 4,7,10-trioxatridecan-1,13-diamine, 2-methoxyethylamine,2-ethoxyethylamine,3-meth3xypropyl-amlne,3-ethoxypropylamlne,3-~2-ethylhexoxy)propylamine, 3-(2-methoxyethoxy)propylamine, 2-methoxyphenylethyl-amlne, 4-methoxyphenylethyl d ne and homoveratrylamine.
- 6 - O.Z. 0050/43579 Secondary amines III and III' are, for example:
Secondary amines without ~urther heteroatoms are, for example: dLmethylamine, diethylamine, di-n~propylamine, di-isopropylamine, di-n-butylamine, di-(2-methylpropyl)-S amine, di-tert-butylamine, di-n-pentylamine, di-(2-methylbutyl)amin~, di-(3-methylbutyl)amine, di-(2,2-dLmethylpropyl)amine, di-(3,3 dimethylpropyl)amine, di-n-hexylamine, di-2-ethylhexylamine, di-tridecylamine, N-methylbutylamine, N-ethylbutylamine, diallylamine, dicrotylamine, dLmethallylamine, dicyclopropylamine, dicyclopentylamine, ~-methylcyclohexylamine, N-ethyl-cyclohexylamine, dicyclohe~ylamine, N-methylaniline, N-ethylaniline and diphenylamine.
Secondary amine~ III and I}I' containing further heteroa~om sub~tituent~ ar~, for example:
Diethanolamina, di-isopropanolamine, methylethanolamine, ethylethanolamine, butylethanolamine, cyclohe~yl-ethanolamine, hydroxyothylaniline and di-2-methoxyethyl-amine.
- Hydrogenation of unsaturated amine~ :
~he unsaturated amine~ I obtained from reacting - -ammonia or primary or ~econdary amine~ III and 2-alkenal~
II can be hydrogenated on customsry hydrogenation catalysts æuch as palladium, platinum, ruthenium, 2~ rhodium, cobalt, nickel and copper as a metal or metal mixtura or o~ a support material such a~ alumina,-silica, activ~ carbon, zirconium o~ide or titanium dioxide, in particular on palladium as metal or on a support material ~uch a3 alumina, silica or ac~ive carbon, without working up and in the presence of the water of reaction, preferably without working up and without remoYing ~he water o~ reactionp to give tho corre~pond~ng ~aturated 1,3-diami~e~ IV. The u~saturated amine~ I' prepared by amine exchange reaction can equally be hydrogenated, pre~erably withou~ working up ~he crude : produc~. -The hydrogenation can be carried out in the ,.
_ 7 _ O.Z. 0050/43579 pre~ence or ab ence of inert ~olvent~ such as ether~, for example methyl tert~butyl ether, tetrahydrofuran and dioxane~ or esters, for example methyl acetate and ethyl acetate, at from 0 to 150C, preferably 10 to 80C, particularly preferably 30 to ~0C. The hydrogen pre~ure is from 1 to 350 bar, preferably from 1 to 100 bar.
The ~ub~tituent~ Rl, R2, R3, R~, Rg, R6 and R7 in the compounds of the general formulae I, I~, II, III, III' and IV have the following meanings:
n 1 ~2 R3 R4 Rs R6 R7 e R ,~ , , , , , ar - hydrogen, - Cl- to C20-alkyl, preferably Cl- to Cl2-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, i~obutyl, sec-bu~yl, tert-kutyl, n-pentyl, isopentyl, sec-pentyl, neo-penty~, 1,2-dimethylpropyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl and i~ododecyl particularly prefsrably Cl- to C~-alkyl such as methyl, ethyl, n-propyl, i opropyl, n-butyl, isobutyl, sac-butyl and tert-butyl, - C2- to C20-alkenyl, preferably C2- to Cl2-alkenyl such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, ~ec-butenyl, tert-but2nyl, n-pen~enyl, isopenten~l, sec-pentenyl, neo-pentenyl, 1,2-dimethenylpropenyl, n-hexenyl, isnhexenyl, sec-hexenyl, n-heptenyl, isoheptenyl, n-octenyl, i~ooctenyl, n-nonenyl, isononenyl, n-decsnyl, isodecenyl, n-undecenyl, isoundecen~l, n-dodecenyl and isodcdecanyl, particularly preferabl~ C~- to C4-alkenyl ~uch as e~henyl, n-propenyl, : 30 isopropenyl, n-butenyl, i obutanyl, sec-butenyl and ter~-butenyl, : - C3- to C8-cycloalkyl such a~ cyclopropyl, cyclobutyl, cy¢lopentyl, cyclohexyl, cycloheptyl and cyclooctyl, :
preferably cyclopentyl, cyclohexyl and cyclooctyl, particularly preferably cyclopentyl and cyclohe~yl, - C3- to C8-cyeloalkenyl i~iuch as cyelopropenyl, cyclo-butenyl, cyelopentenyl, cyclohexenyl, cyclohept~nyl and , ' :', ,: ': ', '' ' ' ' ' ' '.' ;' ' ' , : ' ' , ' ~.:, ' ' ' '. '': , ~' :', - ' ' " '' ', .' ";' ' ' . ' ' '' ' "" '. ' . ' ~ ': '' ' : ' ' , ' ' , . ' :' ~ ' , ', : . : ' ' , . i' , , ' . " . " : ' ',, , . ~' .' ', ' , ~' " ~ ,,'' ' '' , " ' ' ' ' ' ' ' 2 ~
- 8 - O.z. 0050/~3579 cyclooctentyl, preferably cyclopentenyl, cyclohexenyl and cyclooctenyl, - phenyl, - C7- to C20-phenylalkyl~ preferably C7- to C~2-phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, 1-phenylbutyl, 2 phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl, 1-phenethyl and 2-phenethyl, - C1- to C20 alkoxy, preferably C,- to C12-alkoxy ~uch a~
methoxy, ethoxy, n-propoxy, i opropoxy, n-butoxy, i~obutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, sec-pentoxy, neo-pentoxy, 1,2 dimethyl-propoxy, n-hexoxy, isohexoxy, cec-he~oxy, n heptoxy, i~oheptoxy, n-octoxy, i900CtoXy~ n-nonoxy, isononoxy~ n-decoxy, isodecoxy, n-undecoxy, i~oundecoxy, n-dodecoxy and isododecoxy, particularly preferably C1- to ~4-alkoxy such as methoxy, ethoxy, n-propoxy, isopropcxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy~
- phenoxy, - C7- to C20-phenoxyalkyl, preferably C7- to C12-phenoxyalkyl such as benzoxy, l-phenoxyethyl, 2-phenoxyethyl, 1-phenoxypxopyl, 2-phenoxypropyl, 3-phenoxypropyl, 1-phenoxybutyl, 2-phenoxybutyl, 3 phenoxybutyl and 4-phenoxybutyl, particularly preferably benzoxy, 1 phenoxysthyl and 2-phenoxy~thyl, - C~- to C20-alkylamirlo, preferably Cl- to Cl2-alkylamino such a~ methylamino, ethylamlno, n-propylamino, i~opropylamlno, n-butylamino, isobutylamino, sec-butqlamino, ter~-butylsmino, n-pentylamino, isopentylamino, sec pentylamino, n~o pentylamino, 1,2-dimethylpropylamino, n-hexylamino, i~ohexylamino, sec-hexylamino, n-heptylamino, isoheptylamino, n-octylamino~ isooctylamino, n-nonylamino~ isononylamino, n-decylamino, isodecylamino, n-undecylamino, isoundecylæmino, n-dodecylamlno and i~ododecylamino, particularly preferably Cl- to C4-alkylamino such a~
- , . ,.. , ., . , ~ . . , . , .. ,: : : , : ; ; ;
-` 2~1Q~
_ g _ o.z. 0050/43579 methylamino, ethylamino, n-propylamino t isopropylamino, n-butylamino, isobutylamino, sec-butylamino and tert-butylamino, - phenylamino, - C7- to CzO-phenylalkylamino, preferably C7- to Cl2-phenylalkylamino ~uch as benzylamino, l-phen ethylamino, 2-phenethylamino, l-phenylpropylamino, 2-phenylpropylamino, 3-phenylpropylamino, l-phenyl-butylamino, 2-phenylbutylamino, 3-phenylbutylamino and 4-phenylbutylamino, particularly preferably benzylamino, 1-phenethylamino and 2-phenethylamino, - pyridyl, - imidazolyl or R~ and R2 or Rl and R3 or R2 and R3 together are a C2- to C8-alkylene which ~ 8 unsub~tituted or mono- to pentasubstituted by Cl- to C4-alkyl or un ub~ti~uted or mono~ub~tituted to tetra~ub~tituted by amino, N-Cl- to C3-alkylamino, N,N-Cl- to C~-dialkylamino, hydroxyl, O-C1- to C~-alkylamino and/or Cl- to C8-alkoxycarbonyl, such as aminoalkyl, N-methyl-aminoalk~ ,N-dLmethylamino-alkyl, N-ethylaminoalkyl, N,N-diethylaminoalkyl, methoxyal~yl and ethoxyalkyl, preferably aminoethyl, N-methylaminoethyl, N,N-dimethylaminoethyl, aminopropyl, N-methylaminopropyl, N,N~dimethylaminopropyl, h~dro~yethyl, methoxyethyl, ethoxyethyl, hydroxypropyl, methoxypropyl and ethoxypropyl.
~ he ~ollowing may be men~ioned a~ novel 1,3-diamines IV-N,N~-2-trima~hyl 1,3-propanediamine, N,N,~,N~-~etra-ethyl-2 methyl-1,3-propanediamine, N,~-di-n-propyl-2-methyl-1,3-propanediamine, N t N,N~,N~-tetra-n-propyl-2-methyl-1,3-propanediamine, N,N'-di-i-propyl-2-methyl-1,3-propanediamine, N,N'-di-n-butyl-2-me~hyl-1/3-propane-diamine, N,N,N~,N'-tetra-n-butyl-2-methyl-1,3-propane~
diamine, N,N'-dicyclohexyl-2-methyl-1,3-propanediamin0, N,N'-di~2-ethylhaxyl)-2-methyl-1,3-propanediamine, N,N,~'/N'-tetra(2-ethylhexyl)-2-methyl-1,3-propanedi-....... . . .
.. ! , " . , ' . , ~ : " . ~ , .. , ., . ,~
- 10 - O.Z. 0050/43579 amine, N,N~-di(2-hydroxyethyl) 2-methyl-1,3-propanedi-amine, N,N'-di(3 hydroxypropyl)-2-methyl-1,3-propanedi ~
amine, N,N'-di(3-methoxypropyl)-2-methyl-1,3-propanedi-amine, N,N'-di(N,N-dimethyl-2-aminoethyl)-2-methyl 1,3-propanediamine, N,N'-di(N,N-dimethyl-3-am~nopropyl)-2~methyl-1,3-propanediamine, N,N'-diphenyl -2-methylo 1,3-propanediamine, N,N~-dibenzyl-2-methyl-1,3-propane-diamine, di(N-i-propylamino-2-methylpropyl)-1,6-hexarldi-arnLne, N-cyclohexyl-N'-i-propyl-2-methylpropane-1,3-diamine, N,N~-di-n-propyl-N'-i-propyl-2-methylpropane-1,3-diam~ne, N-i-pxopyl-N'-phenyl-2-methylpropane-1,3-diamine, propyl-N~-(2-hydroxyethyl)-2-methylpropane-1,3-diamine, N-i-propyl-N '-(3-hydroxypropyl)-2-methylpropane-1, 3-diamine, N-i-propyl-N' (3 mathoxypropyl)-2-methyl-propane-1,3-diamine, N-i-propyl-N'-(3-methylam~nopropyl)-2-methylpropane-1,3-diamine, N-i-propyl~ 3-dimethyl-am~nopropyl)-2-methylpropane-1,3-diam~ne, 11,14-dimethyl-1,5,9,13-tetraazapentadecan, 1-cyclohexylamino-2-methyl-3 piperidylpropane, 2-methyl-1-piperidyl 3-i-propylamino-propane, 2-methyl-1-morpholino-3-i-propylaminopropane, 2-methyl- 1-morpholino-3-piperidylpropane, 2,5,12,15-tetramethyl-3,7,10,14 tetraazahexadecan, 2,5,16, 19-tetramethyl-3,7, 14y 18-tetraa~aeicosan, 2,5,17,20-tetramethyl-3,7,11,15,19-pentaazaheneicosan, N,~'-di-t-butyl-l,3-propanediamine, ~,N'-di-t-butyl-2-ethyl-1,3-propanediamine, N,~ di-t-butyl-2-n-nonyl-1,3-propanediamine, N,N'~di-i-propyl~l,3-butanediamine, M,N'-di-n-butyl-1,3-butanediamirle, N,N '-di-n-butyl-2-n-propyl-1,3-pentanedia~Line, 1~,N'-di-i-propyl-1,3-butanedi-am~ne.
N,N' -alkyl-~ub tituted 1,3-propanediamine~ are u~ed, for example, in the preparation of CFC-free polymer~, ae catalyst~ for polyurethanes and curing ;~gen~s, e.g~ for epoxy resin3, a~ components or additive~ in the prepara-tion o c:ertain types o~ nylon, as ~tarting materials for polyurea~ or in the preparation of iEinishing agents for 2'~
- 11 - o.z. oOsO/43579 textile fibers and for adhesives.
EXAMPLES
- Preparation of unsaturated amine~ I and subsequent hydrogena~ion 26.3 g (0.375 mol) of methacrolein were added dropwise over an hour to 88.5 g (1.5 mol) of isopropylamine such that the temperature does not rise above 35C. qlhe mixture i~ stirred at 40C for an hour and the crude isopropylaminQ~methacrol~in condansation product is hydrogenated over 3 g of palladium on active carbon ~10% Pd) at 50C and 100 bar of hydrogen until ab~orption of hydrosen i~ complete. Fractional di ~illation (b.p.- 100C/25 mbar) yielded 52 g ~81 %3 of N,~'-dii~opropyl-2-methyl 1,3-propanediamine.
26.3 g (0.375 mol) of methacrolein were added dropwise over an hour to 88.5 g (1.5 mol) of isopropylamine such that the temperature doe~ not rise above 45~C. The mixture i~ ~tirre~ at 40C for an hour and the crude isopropylamine!methacrolein condensation product i8 hydrogenated over 0.5 g o~ palladium on active carbon (10 % Pd) at 50C and a hydrogen pre~surs of 100 bar until absorption of hydrogen i~ complete. Fractional distillation (b.p.: 100C/25 mbar) yialded 52 g (81 ~) of N,N~-diisopropyl-2-methyl-1~3-propanediamine.
EXA~P~ 3 61.3 g (0.875 mol3 of methacrolein were added dropwi~e over an hour ~o 2Q6.5 g (3.5 mol~ of isopropylamine ~uch ~hat the ~mperature does not ri~e above 35C. The mixture is stirred at 40C for an hour and the crude isopropylamine/methacrolein condena~ion product i~ hydrogenated over 5 g of palladium on active : carbon (10~ Pd) at 25C an~ atmo3pheric pre~ure until ah80rption of hy~ro~en i~ complete. ~ractional distillation (b.p.: 98C/20 ~bar) yieldad 118 g (79%) of N,N'-diisopropyl-2-mothyl-1,3-propanediami~e.
.
. : . , . .. : . , 21~ j~OO
- 12 - O. Z . ~050/43579 EXA~LE 4 105 ~ (1.5 mol) o~ methacrolein were added dropwise over an hour to 3.54 g (~ mol) of isopropylamine such that the temperature does not ri~e above 45C. The mixture is 3tirred at 40C for an hour and thP crude i~opropylamine/methacrolein condensation product i~
hydrogenated, after diluting with 400 ml of tetrahydxofuran, over 15 g of palladium on active carbon (10 ~ Pd) at 50C and 100 bar of hydrogen until absorp-t~on of hydrogen is complete. Fractional distillation(b.p.: 98C/20 mbar) yielded 212 g ~83%) of N,N'-diiso-propyl-2-methyl-1,3-propanediamine.
EXANPLE ~
By a method 3imilar to Example l, 310 g (83 %) of N,N~-di-n-bu~yl-2-m~thyl-1,3-propanedia~ine (b.p.:
97C/1 mbar) were obtained from 140 g (2 mol) of methacrolein and 672 g (8 mol) of n-bu~ylamine (molar ratio 1 : 4) ovar 15 g of palladium on active carbon (10%
Pd)- . .
By a mathod similar to Example 4, 346 g (87 %) of N,~'-di-tert-butyl-2-methyl-1,3-propanediamine (m.p.:
58C; b.p.s 106C/lS mbar) were obtained from 140 ~ (2 mol) o~ methacrolein and 504 g (6 mol) o~ tert-butylamine (molar ratio 1 : 3) over lS g of palladium on active carbon (10 % Pd~.
. EXA~PL~ 7 B~ a method ~imilar to Example 1, 459 g (83 %) of N,N'-dicyclohexyl-2-methyl-1,3-propanediamine (b.p.: 150 to 160~C/1 mbar) were obtained fro~ 153.5 g (2.2 mol~ of met~acrolein and 870 g (8.8 mol) o~ cyclohe~ylamine (molar ratio 1 : 4 ) over 15 g of palladium on active carbon (10 ~ Pd~.
By a method ~imilar to Example 1~ 398 g (87 ~) of N,N'-di-t2~ethylhexyl)-2-methyl-1,3-propanediamine (b.p.: 170C/1 mbar) were obtained from 100 g (1.5 mol) :, ... ,:: , , .. , :, :: . . . . .......................... .. . - .~:
., .. . , ,. .................. ,, ,,.. .. . . : ... : ., : : . . . . . - . . .. . , . , ., , ~ . ,.. . : . , : .. .: . .. ..
` - 13 - O.z. OOS0/43579 of me~hacrolein and 754 g (5.8 mol) of 2-ethylhexylamine (molar ratio 4 : 1) over 15 g of palladium on active carbon (10 ~ Pd).
E~AMPLE 9 By a method ~ ~ilar to Example 1, 76 g (20 %) of N,N'-dibenzyl-2~methyl-1,3 propanediamine (b.p.: 59C/1 mbar) were obtained from 112 g (1.6 mol) of methacrolein and 686 g (6.4 mol) of benzylamine (molar ratio 4 : 1) over 10 g of palladium on astive carbon (10 ~ Pd).
By a method ~imilar to Example 1, 376 g (73 %) of N,N'-di-(N,N-dimethyl-3~aminopropyl)-2-methyl-1,3-propanediamine ~b.p.: 159C/5 ~bar) were obtained from 140 g (2 mol) of methacrolein and 816 g (8 mol) of N!N-dimethylprop~lenediamin2 (molar ratio 4 : 1) over 15 g o~
palladium on active carbon (10 % Pd~.
EXA~PLE 11 By a method ~imilar to Ex~mple 1, 167 g (64 ~) of N,N'-di-(2-aminoethyl~-2-methyl-1~3-diaminopropane (b.p.: 118 to 130Ctl mbar) were obtained from 102 g (1.5 mol) of methacr~lein and 901.5 g (15 mol) of ethyl-enediamine (molar ratio 1 : 10~ over 15 g of palladium on active carbon (10 ~ Pd).
By a m~thod ~imilar to Ex~mple 1, 310 g (59 %) of N,N'-di-(2~hydroxyethylj-2-methyl-1,3-propanadiamine (b.p.: 162 to 172C/1 mbar).were obta~ned from 140 g (3 mol) of methacrolein and 488 g (8 mol3 o~ ethanolamine (molar ratio 1 : 4) over 15 g of palladium on active 3Q carbon (10 % Pdj.
.' ~XANPL~ 13 By a method similar to Example 1, 350 g (69 %) of N,~'-di (2-methoxyethyl)-2~methyl 1,3-propaned~amine (b.p.~ 96C/1 mbar) were obtained from 17S g (2.5 mol) of methacrolein and 750 q (10 mol) of me~hoxyethylamine (molar ratio 1 : 4) over 15 g of palladium on active - ,, ~ , :,, - -. , .,: ,. . . . ..
, , ,:::, ~. . . . . . .
~1~5~
- 14 - O.Z. 0050/43579 carbon (10 % Pd).
By a method sLmilar to Example 1, 150 g (60 %) of N,N'-dii~opropyl-1,3~butanediamine (b.p.: 43C) were 5obtained from 102 g (1.5 mol) of crotonaldehyde and 344 g (5.8 mol) of isopropylamine (molar ratio 1 : 4) over 10 g of palladium on active carbon (10 ~ Pd).
By a method ~imilar to Example 1, 162 g (81 ~) of 10N,N'-di-n-butyl-1,3-butanediamine (b.p.: 120C/18 mbar) were obtained from 70 g (1 mol3 of crotonaldehyde and 584 g (8 mol) of N-butylamine (molar ratio 1 : 8) over 15 g of palladium on active carbon (10 ~ Pd).
15By a method ~Lmilar to ExEmple l, 440 g (67 %) of N,N'-di-tert-~u~yl-2-nonyl-1,3-propanediami~e (b.p.: 150C/1 mbar) w~r~ obta$ned from 546 g (2.1 mol3 of 2-nonylacrolein (a~ a 70 % strength ~olu~ion in decane) a~d 444 g (6 mol~ of tert-butylamine ~molar ratio 201 : 3) over 15 g of palladium on active carbon (10 % Pd).
EXAMPL~ 17 By a method similar to Example 1, 395 g (84 %) of N,N'~di-tert-butyl-1,3-propanediamine (b.p. 5 132C/
100 mbar) ware obtained from 140 g (2.5 mol) of acrolein 25and 732 g (10 mol) of tert-butylamine (molar ratio 1 : 4) over I5 g of palladium on active carbon (10 ~ Pd).
. E~AMPL~ 18 : ~By a~method ~imilar to ~ample 1, 29 g ~80 ~) of 1,3-dipiperidyl-2-methylpropane (b.p.: 90 ~o 30: 100C/l mbar) were obtained from 10 g (0.14 mol) of mathacrolein and 50 g (0.6 mol) of piperidine (molar :~ ratio 1 s 4.2) over 2 g of Pd on active carbon (10 % Pd3.
EXANP~ I9 By a method ~imilar to Example 1, 250 g (40 %) of 35N~N~N',N'-tetra-n-butyl-2-methyl-1,3-propa~ediamine (~.p.: 125C/1 mbar) were obtained from 140 g (2 mol) of methacrolein and 155 g (12 mol) o~ di n-butylamine (molar '' ~
' " ,.
- 15 - O.~. 0050/43579 ratio 1 : 6) over 15 g of Pd on active carbon (10 % Pd).
By a method similar ~o Example 1, 149 g (50 %) of N,N,N',N'-tetra-n-propyl-1,3-propanediamine (b.p.: 137C~
5were obtained from 68 g (1.2 mol) of acrolein and 740 g (7.3 mol) o~ di-n-propylamine (molar ratio 1 : 6) ovar 15 g of Pd on active carbon (10 % Pd).
COMP MISON EXAMPLE
According to J. Am. Chem. Soc. 74, tl952) 2016 to 102018 Table 1, 10th example 35 g (0.5 mol) of methacrolein were added dropwise over an hour to a solution of 25 g of anhydrou~
pota~sium carbonate in 147.5 g (2.5 mol) of isopropylamine and from 5 to 10QC.-After filtering off 15the pota~sium carbonate, the crude isopropylamine/-methacrolein conden~ation product wa~ hydroge~ated over 5 g of Raney ~ickel freed from water at 105C and 70 bar of hydrogen over 6 h. Fractional distillation (b.p.: 80-100C/35 mbar) yielded 47 g ~50 ~i) of N,~'-diisopropyl-2-2~methyl-1,3-diamlne. The literature yield is 58 %.
Examples of the continuoue hydrogenation of the Schiff ~ 9 base~:
EXAMPL~ 21 A vertically arranged tubular reactor ~diameter:
2514 mm, packing height: 50 cm, oil-heated double jaak~t) wa~ packed with 75 ml (47.6 g~ of a catalyst containing O.5 % Pd on y-alumina in the form of 4 mm strands (preparation of cataly~t by pora LmmersiOn of yoalumina using aqueou~ palladium nitrate ~olution and drying at 30120~C). The catalyst i9 reduced ln situ.
20 g of a ~olution of 155 g (2.6 mol) of iscpropylamine and 61 g (0.88 mol) of methacrolein in -200 g of t~trahydrofuran are pa~ed through the reactor hourly from the bottom upward~. 10 (s~t~pO) of hydrogen 35are pa~sed through th~ reactor hourly at a pre~ure of 80 bar. The temperature i8 70C. The: di~charged reactio~
produat i8 decompreY~ed to atmospheric pre3sur~. The .
, - 16 - O.Z. 0050/43579 yield of N,N' diisopropyl-2-methyl-1,3-diaminipropane i~
80 %.
EXAMP~E 22 N,N,N',N',2-pentamethyl-1,3-diamlnopropane A vertically arranged tu~ular reactor (diameter:
14 mm, packing height: 50 cm, oil-heated double jacket) wa~ packed with 75 ml (47.6 g) of a cataly~t containing O.5 ~ Pd on y-alumina in the form of 4 mm ~trands (preparation of catalyst by pore imm~r~ion of ~-alumina . using aqueous palladium nitrate ~olution and drying at 120C). The cat~ly~t i~ reduced in ~itu.
lOQ ml of a 20% strength ~olution of methacrolein in tetrahydro~uran and 60 ml of dimethylamine are pa~ ed through the reactor hourly from the bottom upward~. 10 (~.t.p.) of hydrogen are pa~ed through the reactor hourly at a pre ~ur~ of 75 bar. The temperature is 70C.
The discharged reaction product is decompressed to atmo~pheric pressure, fr2ed from dL~ethylamlne and distiIled. Tha di~charged reaction product collected over the course of an hour yield~, after distillation at 70C/100 mbar, 28 g of N,N,N~ 2-pe~tamethyl-1,3-diaminopropane. Ths yield iB 85 96.
- Transam~nation of the unsaturated amines I and ubsequent hydrogenation EXA~hl~ 23 168 g t 2, 4 mol ) of methacrolein were added dropwi~e in th~ course of an hour to 354 g l6 mol3 of i~opropylamine uch that the temperature doe~ not exc:eed 35C~ Ths mixtur~ i~ stirred at 40C for an hour. This crude i~opropylamine/methacrol~i~ conden~ation product i~
treated at 40C with 287 g (2.9 mol) of cyclohexylamine and i~opropylamlne i~ sLmultaneou~ly di~tilled o~f. The un~ymmetrically ~ubst~tuted diamine precursor thus o~tained i~ diluted with 400 ml o~ tetrahydrofuran and hydrogenated over 15 g of Pd on active carbon (10 % Pdj at 50C and 100 bar until absorption o~ hydro~en i~
completo. Practional di tillation (b-p-. 99 to , .
. : , -,, ~
. ~
- 17 - O.Z. OOS0/43579 106C/1 mbar) yielded 311 g (73 ~) of N-iRopropyl-N'-cyclohexyl-2-methyl-1,3-propanediamine.
EX~MPLE 24 By a method ~imilar to Example 23, 191 g (52 %) of 11,14-dimethyl-1,5,9,13-tetrsa2apentadecan (b.p.: 188 to l90~C/5 mbar) were obtained from 105 g (1.5 mol) of methacrolein, 267 g (4.5 mol) of isopropylamine and 196.5 g (1.5 mol) of dipropylenetriamine (molar ratio 1 : 3 : 3) over 15 g of active carbon (10 % Pd) and in 400 ml of tetrahydrofuran.
~XAMPLE 25 By a method similar to Example 23, S3 g (52 %) of dl~ isopropylamino-2-methylpropyl)-1,6 hexanediamine (~.p.s 170C/1 mbar) wsre obtained from 50 g (Q.71 mol) of methacrolein, 176 g ~2098 mol) of isopropylaminQ and 41.5 g (0.35 mol) o~ hexamethylsnediamine (molar ratio 2 : 8 : 1) over 5 g of palladium on active carbon (10 % Pd) and in 50 ml of tetrahydrofuran.
By a method sLmilar to Ex2mpla 23, 171 g (51 %) of N-isopropyl-N'-(N-methyl-3-aminopropyl)-2-methyl-1,3-propanediamine (B.P.: 90 to 96C/l mbar) were obtained from 116 g (1.7 mol) of methacrolein~ 245 g (4.2 mol) of isopropylamine and 176 g (2 mol) of N-methylpropylenedi-amino (molar ratio 1 : 2.5 ~ ) over 10 g of palladium on acti~e carbon (10 ~ Pd ) a~ in 40Q ml of tetrahydro-furan.
: EXANPLE 27 By a method similar to exampl~ 23, 61 g (47 %) o~
1-i~opropylamino-2-me~hyl-3-morpholinspropane (b.p.s 75~C) wers obtained from 61.3 g (0.78 mol) o methacrolein, 206 g (3.5 mol) of i~opropylamine and 76 g (0.8~ mol) of morpholin~ (mol~r ratio 1 : 4 ~ 1) over 10 g of palladium on active carbon (10 ~ Pd).
3S E~ 28 By amethodsimilar to E~cample 23, 56 g (50 %) of l-cyclohexylamino-2-methyl-3-piperidylpropane , ' :. ' ' . ' ' ' . . .'. ' .
- c2~J ~
`18 - O.Z. 0050/43579 (b.p.. 120C/1 mbar) were obtained from 35 g (0.5 mol) o me~hacrolein, 170 g (2 mol) of piperidine and 43.5 g (0.5 mol~ of cyclohexylamine (molar ratio 1 : 4 : 1) over 3 g of Pd on active carbon (10 ~ Pd) and in 50 ml of S tetrahydrofuran.
By a method ~imilar t~ Example 23, 17 g (16 %) of l-morpholino-2-methyl-3-piperidylpropane (b.p.~ 110C/
1 mbar) were obtained from 35 g (0.5 mol) of 10methacrolein, 170 g (2 mol) of piperidine and 43.5 g (O.S mol) of morpholine (molar ratio 1 : 4 : 1~ over 3 g of Pd on ac~ive carbon (10 % Pd).
' , ' .. ... .
- , ., . . ., , . . ~..... .. ", . , : . , . .. ; . ...
.. ,: ., . . ~. . , .. . . . : , . . ,, :. ~, :.. 1 ., .. , . , . .,; . , .. :
Claims (4)
1. A process for preparing unsaturated amines of the general formula I
(I), where R1,R2,R3,R4,R5 are hydrogen, C1- to C20-alkyl, C2- to C20-alkenyl, C3- to C8-cycloalkyl, C3- to C8-cycloalkenyl, phenyl, C7- to C20-phenyl-alkyl, C1- to C20-alkoxy, phenoxy, C7- to C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino, C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or R1 and R2 or R1 and R3 or R2 and R3 together are a C2- to C8-alkylene which is unsubtituted or monosubstituted to pentasubstituted by C1-to C4-alkyl or unsubstituted or monosub-tituted to tetrasubstituted by amino, N-C1- to C8-alkylaminol N,N-C1- to C8-di-alkylamino, hydroxyl, O-C1- to C8-alkyl-amino and/or C1- to C8-alkoxycarboxyl, and X is =C-N(R4R5) or -C=N-R4, by reacting 2-alkenals of the genhral formula II
(II), wherw R1, R2 and R3 have the abovementioned meanings, with ammonia or primary or secondary amines of the general formula III
(III), where R4 and R5 have the abovementioned meanings, at from (-20) to 70°C and pressures from 0.01 to 100 bar, which comprises carrying out the reaction without removing the water of reaction.
(I), where R1,R2,R3,R4,R5 are hydrogen, C1- to C20-alkyl, C2- to C20-alkenyl, C3- to C8-cycloalkyl, C3- to C8-cycloalkenyl, phenyl, C7- to C20-phenyl-alkyl, C1- to C20-alkoxy, phenoxy, C7- to C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino, C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or R1 and R2 or R1 and R3 or R2 and R3 together are a C2- to C8-alkylene which is unsubtituted or monosubstituted to pentasubstituted by C1-to C4-alkyl or unsubstituted or monosub-tituted to tetrasubstituted by amino, N-C1- to C8-alkylaminol N,N-C1- to C8-di-alkylamino, hydroxyl, O-C1- to C8-alkyl-amino and/or C1- to C8-alkoxycarboxyl, and X is =C-N(R4R5) or -C=N-R4, by reacting 2-alkenals of the genhral formula II
(II), wherw R1, R2 and R3 have the abovementioned meanings, with ammonia or primary or secondary amines of the general formula III
(III), where R4 and R5 have the abovementioned meanings, at from (-20) to 70°C and pressures from 0.01 to 100 bar, which comprises carrying out the reaction without removing the water of reaction.
2. A process for reacting unsaturated amines I as claimed in claim 1 to give the unsaturated amines I' (I '), where R1, R2, R3, R4 and R5 have the abovementioned mean ings and X' is =C-N(R6R7) or -C=N-R6 and R6 and R7 have the meanings given for R1 to R5, which comprises reacting the unsaturated amines I with primary or secondary amines of the general formula III' (III'), where R6 and R7 have the meanings given for R1 to R5, at from 20 to 150°C.
3. A process for hydrogenating unsaturated aminee I
or I' as claimed in claim 1 or 2, which comprises hydro-genating the unsaturated amines I or I' under a hydrogen pressure from 1 to 350 bar at from 0 to 150°C.
or I' as claimed in claim 1 or 2, which comprises hydro-genating the unsaturated amines I or I' under a hydrogen pressure from 1 to 350 bar at from 0 to 150°C.
4. A 1,3-diamine of the general formula IV
(IV), where R1,R2,R3,R4,R5,R6,R7 are hydrogen, C1- to C20-alkyl, C2- to C20-alkenyl, C3 to C8-cycloalkyl, C3- to C8-cycloalkenyl, phenyl, C7- to C20-phenylalkyl, C1- to C20-alkoxy, phenoxy, C7- to C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino, C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or and R2 or R1 and R3 or R2 and R3 together are a C2- to C8-alkylene which is unsubtituted or monosubstituted to pentasubstituted by C1- to C4-alkyl or unsubstituted or monosubstitutad to tetrasubstituted by amino, N-C1- to C8-alkylamino, N,N-C1- to C8-dialkylamino, hydroxyl, O-C1- to C8-alkylamino and/or C1- to C8-alkoxycarbonyl, with the proviso that R1 and R2 are not hydrogen if R3 is methyl and R4 and R5, R6 and R7 are in each case hydrogen or methyl, R4 and R5 are hydrogen and R5 and R7 are ethyl and also R4 and R5, R6 and R7 are in each case together (CH2)5 or (CH2)2 O-(CH2)2.
(IV), where R1,R2,R3,R4,R5,R6,R7 are hydrogen, C1- to C20-alkyl, C2- to C20-alkenyl, C3 to C8-cycloalkyl, C3- to C8-cycloalkenyl, phenyl, C7- to C20-phenylalkyl, C1- to C20-alkoxy, phenoxy, C7- to C20-phenoxyalkyl, C1- to C20-alkylamino, phenylamino, C7- to C20-phenylalkylamino, pyridyl or imidazolyl, or and R2 or R1 and R3 or R2 and R3 together are a C2- to C8-alkylene which is unsubtituted or monosubstituted to pentasubstituted by C1- to C4-alkyl or unsubstituted or monosubstitutad to tetrasubstituted by amino, N-C1- to C8-alkylamino, N,N-C1- to C8-dialkylamino, hydroxyl, O-C1- to C8-alkylamino and/or C1- to C8-alkoxycarbonyl, with the proviso that R1 and R2 are not hydrogen if R3 is methyl and R4 and R5, R6 and R7 are in each case hydrogen or methyl, R4 and R5 are hydrogen and R5 and R7 are ethyl and also R4 and R5, R6 and R7 are in each case together (CH2)5 or (CH2)2 O-(CH2)2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4232424A DE4232424A1 (en) | 1992-09-28 | 1992-09-28 | Process for the production of unsaturated amines |
| DEP4232424.6 | 1992-09-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2105100A1 true CA2105100A1 (en) | 1994-03-29 |
Family
ID=6468999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002105100A Abandoned CA2105100A1 (en) | 1992-09-28 | 1993-08-30 | Preparation of unsaturated amines |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0590419A1 (en) |
| JP (1) | JPH06263697A (en) |
| CA (1) | CA2105100A1 (en) |
| DE (1) | DE4232424A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705699A (en) * | 1994-03-04 | 1998-01-06 | Basf Aktiengesellschaft | Preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| CN102203054A (en) * | 2008-11-05 | 2011-09-28 | 巴斯夫欧洲公司 | Method for producing n,n-substituted-3-aminopropan-1-ols |
| US8461391B2 (en) | 2008-05-13 | 2013-06-11 | Basf Se | Method for producing N,N-substituted-1,3-propandiamines |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19956786A1 (en) * | 1999-11-25 | 2001-05-31 | Basf Ag | New optically active aminoalcohol and diamine derivatives useful as intermediates, e.g. for pharmaceuticals and plant protectants |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2565529A (en) * | 1946-10-18 | 1951-08-28 | Shell Dev | Conjugated aldehyde-secondary amine reaction products |
| DE866647C (en) * | 1947-07-07 | 1953-02-12 | Bataafsche Petroleum | Process for the production of secondary 1,3-alkenediamines |
| CA2026165A1 (en) * | 1989-10-19 | 1991-04-20 | John C. Hansen | Perfluoro-n,n,n',n'-tetrapropyldiaminopropane and use thereof in vapor phase heating |
-
1992
- 1992-09-28 DE DE4232424A patent/DE4232424A1/en not_active Withdrawn
-
1993
- 1993-08-30 CA CA002105100A patent/CA2105100A1/en not_active Abandoned
- 1993-09-16 EP EP93114889A patent/EP0590419A1/en not_active Withdrawn
- 1993-09-27 JP JP5239525A patent/JPH06263697A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5705699A (en) * | 1994-03-04 | 1998-01-06 | Basf Aktiengesellschaft | Preparation of 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
| US8461391B2 (en) | 2008-05-13 | 2013-06-11 | Basf Se | Method for producing N,N-substituted-1,3-propandiamines |
| CN102203054A (en) * | 2008-11-05 | 2011-09-28 | 巴斯夫欧洲公司 | Method for producing n,n-substituted-3-aminopropan-1-ols |
| US8536377B2 (en) | 2008-11-05 | 2013-09-17 | Basf Se | Method for producing N,N-substituted-3-aminopropan-1-ols |
| CN102203054B (en) * | 2008-11-05 | 2014-07-30 | 巴斯夫欧洲公司 | Method for producing n,n-substituted-3-aminopropan-1-ols |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0590419A1 (en) | 1994-04-06 |
| JPH06263697A (en) | 1994-09-20 |
| DE4232424A1 (en) | 1994-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2478858C (en) | Catalysts and method for the production of amines | |
| US8183415B2 (en) | Methods of synthesizing cinacalcet and salts thereof | |
| CN101454304B (en) | Process for the production of benzopyran-2-ol derivatives | |
| EA021623B1 (en) | Supported catalyst and method for producing an amine | |
| JP2004203875A (en) | Production method for amine and use of catalyst in producing the amine | |
| CA2748595C (en) | Process for preparing cinacalcet hydrochloride | |
| MXPA04006141A (en) | Process for the continuous quaternisation of tertiary amines with an alkyl halide. | |
| CA2734971C (en) | Process for preparing cinacalcet | |
| JPH1072454A (en) | Production of n-substituted cyclic amine | |
| CA2105100A1 (en) | Preparation of unsaturated amines | |
| JPH10338664A (en) | Production of tertiary amine from nitrile and secondary amine | |
| US2599001A (en) | Nu, nu-disubstituted-beta-haloalkylamines | |
| EP0908444B1 (en) | A process for producing a tertiary amine having high quality | |
| WO2001077064A1 (en) | Method for the preparation of (e)-n-(6,6-dimethyl-2-hepten-4-ynyl)-n-methyl-1-naphthalenemethanamine (terbinafine) | |
| US8288464B2 (en) | Low-voc polyamines | |
| EP0002148B1 (en) | Compositions containing aminoalkoxyamines, and processes for their preparation | |
| US7875750B2 (en) | Method of obtaining 2-amino-6-alkyl-amino-4,5,6,7-tetrahydrobenzothiazoles | |
| US20020091194A1 (en) | Preparation of primary and secondary amines from nitriles | |
| TW526184B (en) | Process for the cis-selective catalytic hydrogenation of cyclohexylidenamines | |
| US20120165521A1 (en) | Low-voc polyamino alcohols | |
| JPH0428253B2 (en) | ||
| JPS6172734A (en) | Preparation of tertiary amine | |
| US11066354B2 (en) | Process for mono N-alkylation of aminophenol | |
| US7208448B2 (en) | In an amine or nitrile embedded passivated hydrogenation catalyst | |
| JP4145387B2 (en) | Amino alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |