CA2106415C - Process for the preparation of endo/exo-8-n,n-dialkylamino-exo-tricyclo[5.2.1.0 2,6]decane - Google Patents
Process for the preparation of endo/exo-8-n,n-dialkylamino-exo-tricyclo[5.2.1.0 2,6]decaneInfo
- Publication number
- CA2106415C CA2106415C CA002106415A CA2106415A CA2106415C CA 2106415 C CA2106415 C CA 2106415C CA 002106415 A CA002106415 A CA 002106415A CA 2106415 A CA2106415 A CA 2106415A CA 2106415 C CA2106415 C CA 2106415C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- exo
- decane
- reaction
- tricyclo
- 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.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/33—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
- C07C211/38—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton containing condensed ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
- C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
- C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a process for the preparation of endo/exo-8-N,N-dialkylamino-exo-tricyclo[5.2.1.0 2,6]decane by reaction of the corresponding 8-hydroxy compound with a secondary amine in the presence of a hydrogenation catalyst and hydrogen, the water formed during the reaction being removed.
Description
Process for the preparation of endo/exo-8-N,N-dialkyl amino-exo-tricyclo[5.2.1.02~~ decane The invention relates to a process for the preparation of endo/exo-8-N,N-dialkylamino-exo-tricyclo[5.2.1.0z~6]decane from the corresponding 8-hydroxy compound. Quaternary ammonium salts of diaminotricyclo[5.2.1.02'6]decane are used, inter alia, during the preparation of synthetic zeolites as so-called templates, i.e. as molecular negative forms which stabilize the mineral structure during crystallization.
The preparation of 8-N,N-dialkylamino-tricyclo-[5.2.1.02'6]decane is known. P. Wilder et al. (J. Am.
Chem. Soc. 81 (1959), 655 et seq.) prepare this compound ~rom the oxime of 8-ketotricyclo[5.2.1.0z~6]decane, which is reduced with sodium to give 8-aminotricyclo-[5.2.1.02'6]decane. The dimethyl compound is finally obtained in a moderate yield by reaction of the primary amine with a mixture of formic acid and an aqueous formaldehyde solution.
The process described in WO 90/04567 also starts from 8-ketotricyclo[5.2.1.026]decane to obtain 8-N,N-dialkyl-amino-tricyclo[5.2.1.02'6]decane. It is reacted with dialkylformamide (in which alkyl is a methyl, ethyl or propyl radical), in the presence of formic acid in a closed system at 160 to 195°C. The reaction time is 10 to 50 hours.
The known syntheses do not yet meet all the demands made on a process which is to be carried out on an industrial scale. They require the use of expensive chemicals and long reaction times, which impair the economy of the process, and produce the desired product in only a moderate yield.
There was therefore the object of developing a process which avoids the disadvantages described and leads to the desired dialkylamino compound in an industrially simple manner using inexpensive starting substances.
According to the present invention there is provided a process for preparing an endo/exo-8-N,N-dialkylamino-exo-tricyclo[5.2.1.02 6]decane, which process comprises reacting 8-hydroxytricyclo [5.2.1.0 2 6] decane with a secondary amine of the formula HNR1R2, in which R1 and R2 are identical or different and are in each case an alkyl radical having 1 to 6 carbon atoms, at 120 to 250°C in the presence of a hydrogenation catalyst and hydrogen, wherein the water formed during the reaction is removed continuously and the hydrogen is fed to the reaction mixture in an amount of 5 to 300 1 / 1 of catalyst .
The novel process is surprisingly selective and produces endo/exo-8-N,N-dialkylamino-exo-tricyclo(5.2.1.02~6]
decane in a high yield; the amino compound can be isolated from the reaction mixture in a pure form by simple dist i l lat ion .
The 8-hydroxytricyclo[5.2.1.02~6Jdecane employed as the starting compound is a substance which is commercially available and is prepared from tricyclo[5.2.1.0 2 6]deca-3,8-diene (cyclopentadiene) by adding on water in the presence of acid catalysts and subsequent hydrogenation of the hydroxytricyclodecene. It can be used in the commercially available form, i.e., for example, without prior fine purif icat ion .
According to the invention, the hydroxy-tricyclodecane is allowed to react with a secondary amine of the formula HNR1R2. R1 and R2 can be identical or different.
z~os~~5 - 2a -They are alkyl radicals having 1 to 6, preferably 1 to 4, and in particular 1 to 3 carbon atoms. Suitable amines are dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-i-butylamine, di-n-pentylamine, di-3-methyl-butylamine, di-n-hexylamine, di-i-hexylamine, N-methyl-ethylamine, N-methylpropylamine, N-methylbutylamine, N-methyl-pentylamine, N-methylhexylamine, N-ethylpropylamine, N-ethyl-butylamine, N-ethylpentylamine, N-ethylhexylamine, N-propyl-butylamine, N-propylpentylamine, N-propylhexylamine, N-butylpentylamine and N-butylhexyl-amine, in particular dimethylamine, diethylamine and di-n-propylamine, preferably dimethylamine.
The reactants are usually reacted in equimolar amounts;
however, it is also possible to use one of the reactants in excess.
The reaction between the hydroxy compound and secondary amine is carried out in the presence of catalysts.
Although the reaction is not a hydrogenation and hydrogen does not participate directly in the reaction between the starting substances, conventional hydrogenation cata-lysts, for example those based on nickel and cobalt, have proven appropriate for carrying out the reaction. Copper catalysts which, unexpectedly, have an extremely selec-tive action, are employed particularly successfully.
Copper supported catalysts having a copper content of 15 to 85, in particular 50 to 70~ by weight (based on the catalyst) are preferably suitable. They comprise as supports silicic acid, kieselguhr, aluminum oxide, magnesium oxide, carbon or pumice, preferably kieselguhr or aluminum oxide, and if appropriate customary activa-tors and additives, such as magnesium or chromium. The amount of catalyst depends on the content of the hydroxy compound in the reaction mixture. 0.5 to 30, in parti-cular 3 to 20$ by weight of catalyst, based on the hydroxy compound, is usually used. Hydrogen is fed continuously to the reaction mixture in an amount of 5 to 300, in particular 20 to 100 1/1 of catalyst, in order to activate the catalysts and to maintain their activity over the entire reaction time.
The reaction between the reactants proceeds at tempera-tures of between 120 and 250, in particular 145 to 195°C, preferably under normal pressure, although a slight increased pressure of up to 0.1 MPa, in particular up to 0.05 MPa, can be used. According to a proven embodiment, the secondary amine is added to the stirred suspension of 8-hydroxytricyclo [ 5 . 2 .1. 026 ] decane and the catalyst . Both the amine and the tricyclodecane can be employed as a solution, for example using toluene or xylene as the solvent . To ensure that the reaction proceeds rapidly and completely, it is necessary to provide for continuous removal of the water formed during the reaction. This is effected by the processes known in the chemical industry, for example with the aid of a water separator or phase separator, or by azeotropic distillation. The reaction conditions mentioned ensure that the endo/exo isomer is preferentially formed.
The novel procedure can be carried out either contin-ucausly or, in particular, discontinuously.
The endo/exo-8-N,N-dialkylamino-exo-tricyclo[5.2.1.0~~6]-decane is removed from the reaction mixture by simple distillation and is obtained by this procedure in such a pure form that no further purification is necessary for most intended uses.
The preparation of endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.026]decane by the novel process is illus-trated in more detail in the following examples. It is of course not intended to limit the invention to these specific embodiments.
Example 1: Preparation of endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.026]decane 2280 g (15 mol) of 8-hydroxy-tricyclo[5.2.1.026]decane and 228 g of a copper supported catalyst (RCH 60/35;
commercial product from Hoechst AG, Cu content about 60~
by weight, based on the catalyst composition) are initially introduced into a 4 1 three-necked flask provided with a stirrer, thermometer, water separator, reflux condenser and inlet tube, and are heated, while stirring. When a temperature of 100°C has been reached, 20 to 25 1/hour of hydrogen are continuously fed in via -5- ~ 2~oa~~5 the inlet tube to activate the catalyst, and 125 g/hour (2.78 mol) of dimethylamine in gaseous form are simul-taneously fed in via the same inlet tube.
Water is collected in the separator for the first time at a temperature of 14 8 to 150 °C . To accelerate the reac-tion, the temperature is adjusted to 170 to 175°C and the continuous addition of hydrogen and dimethylamine is continued. The water of reaction formed is constantly removed by the separator. After 6 hours, no further discharge of water is observed. 328 g of water of reac-tion are obtained in total, some of the excess dimethyl-amine being dissolved in it.
After cooling, the reaction product is filtered and analyzed by gas chromatography. The crude amine still contains 2 . 98 ~ of residual 8-hydroxy-tricyclo [ 5 . 2 .1. 026 ] -decane, which corresponds to a conversion of about 97~.
The selectivity for endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.026]decane is 80.8, and the ratio of endo to exo compound is 61 : 39.
Example 2 Example 1 is repeated, with the difference that the reaction temperature is 160 to 165°C. The water of reaction formed is again removed from the reaction mixture constantly by the water separator. After 6 hours, no further discharge of water is observed. 312 g of water of reaction are obtained in total, some of the excess dimethylamine being dissolved in this. The cooled and filtered crude amine still contains 3.75 of 8-hydroxy-tricyclo[5.2.1.02'6]decane, according to determination by gas chromatography, which corresponds to a conversion of about 96.2.
The selectivity for endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.0z~6]decane is 80.2, and the ratio of endo to exo compound is 81 : 19. 2 1 0 8 ~ ~ 5 Example 3 Example 1 is repeated, with the difference that the reaction temperature is 150 to 155°C. The water of reaction formed is again removed from the reaction mixture constantly by the separator. After 6 3/4 hours, no further discharge of water is observed. 284 g of water of reaction are obtained in total, some of the excess dimethylamine being dissolved in this. The cooled and filtered crude amine still contains 8.84 of 8-hydroxy-tricyclo[5.2.1.0z~6]decane according to analysis by gas chromatography, which corresponds to a conversion of about 91.28.
The selectivity of endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.02'6]decane is 86.1$, and the ratio of endo to exo compound is 95 . 5.
The preparation of 8-N,N-dialkylamino-tricyclo-[5.2.1.02'6]decane is known. P. Wilder et al. (J. Am.
Chem. Soc. 81 (1959), 655 et seq.) prepare this compound ~rom the oxime of 8-ketotricyclo[5.2.1.0z~6]decane, which is reduced with sodium to give 8-aminotricyclo-[5.2.1.02'6]decane. The dimethyl compound is finally obtained in a moderate yield by reaction of the primary amine with a mixture of formic acid and an aqueous formaldehyde solution.
The process described in WO 90/04567 also starts from 8-ketotricyclo[5.2.1.026]decane to obtain 8-N,N-dialkyl-amino-tricyclo[5.2.1.02'6]decane. It is reacted with dialkylformamide (in which alkyl is a methyl, ethyl or propyl radical), in the presence of formic acid in a closed system at 160 to 195°C. The reaction time is 10 to 50 hours.
The known syntheses do not yet meet all the demands made on a process which is to be carried out on an industrial scale. They require the use of expensive chemicals and long reaction times, which impair the economy of the process, and produce the desired product in only a moderate yield.
There was therefore the object of developing a process which avoids the disadvantages described and leads to the desired dialkylamino compound in an industrially simple manner using inexpensive starting substances.
According to the present invention there is provided a process for preparing an endo/exo-8-N,N-dialkylamino-exo-tricyclo[5.2.1.02 6]decane, which process comprises reacting 8-hydroxytricyclo [5.2.1.0 2 6] decane with a secondary amine of the formula HNR1R2, in which R1 and R2 are identical or different and are in each case an alkyl radical having 1 to 6 carbon atoms, at 120 to 250°C in the presence of a hydrogenation catalyst and hydrogen, wherein the water formed during the reaction is removed continuously and the hydrogen is fed to the reaction mixture in an amount of 5 to 300 1 / 1 of catalyst .
The novel process is surprisingly selective and produces endo/exo-8-N,N-dialkylamino-exo-tricyclo(5.2.1.02~6]
decane in a high yield; the amino compound can be isolated from the reaction mixture in a pure form by simple dist i l lat ion .
The 8-hydroxytricyclo[5.2.1.02~6Jdecane employed as the starting compound is a substance which is commercially available and is prepared from tricyclo[5.2.1.0 2 6]deca-3,8-diene (cyclopentadiene) by adding on water in the presence of acid catalysts and subsequent hydrogenation of the hydroxytricyclodecene. It can be used in the commercially available form, i.e., for example, without prior fine purif icat ion .
According to the invention, the hydroxy-tricyclodecane is allowed to react with a secondary amine of the formula HNR1R2. R1 and R2 can be identical or different.
z~os~~5 - 2a -They are alkyl radicals having 1 to 6, preferably 1 to 4, and in particular 1 to 3 carbon atoms. Suitable amines are dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-i-butylamine, di-n-pentylamine, di-3-methyl-butylamine, di-n-hexylamine, di-i-hexylamine, N-methyl-ethylamine, N-methylpropylamine, N-methylbutylamine, N-methyl-pentylamine, N-methylhexylamine, N-ethylpropylamine, N-ethyl-butylamine, N-ethylpentylamine, N-ethylhexylamine, N-propyl-butylamine, N-propylpentylamine, N-propylhexylamine, N-butylpentylamine and N-butylhexyl-amine, in particular dimethylamine, diethylamine and di-n-propylamine, preferably dimethylamine.
The reactants are usually reacted in equimolar amounts;
however, it is also possible to use one of the reactants in excess.
The reaction between the hydroxy compound and secondary amine is carried out in the presence of catalysts.
Although the reaction is not a hydrogenation and hydrogen does not participate directly in the reaction between the starting substances, conventional hydrogenation cata-lysts, for example those based on nickel and cobalt, have proven appropriate for carrying out the reaction. Copper catalysts which, unexpectedly, have an extremely selec-tive action, are employed particularly successfully.
Copper supported catalysts having a copper content of 15 to 85, in particular 50 to 70~ by weight (based on the catalyst) are preferably suitable. They comprise as supports silicic acid, kieselguhr, aluminum oxide, magnesium oxide, carbon or pumice, preferably kieselguhr or aluminum oxide, and if appropriate customary activa-tors and additives, such as magnesium or chromium. The amount of catalyst depends on the content of the hydroxy compound in the reaction mixture. 0.5 to 30, in parti-cular 3 to 20$ by weight of catalyst, based on the hydroxy compound, is usually used. Hydrogen is fed continuously to the reaction mixture in an amount of 5 to 300, in particular 20 to 100 1/1 of catalyst, in order to activate the catalysts and to maintain their activity over the entire reaction time.
The reaction between the reactants proceeds at tempera-tures of between 120 and 250, in particular 145 to 195°C, preferably under normal pressure, although a slight increased pressure of up to 0.1 MPa, in particular up to 0.05 MPa, can be used. According to a proven embodiment, the secondary amine is added to the stirred suspension of 8-hydroxytricyclo [ 5 . 2 .1. 026 ] decane and the catalyst . Both the amine and the tricyclodecane can be employed as a solution, for example using toluene or xylene as the solvent . To ensure that the reaction proceeds rapidly and completely, it is necessary to provide for continuous removal of the water formed during the reaction. This is effected by the processes known in the chemical industry, for example with the aid of a water separator or phase separator, or by azeotropic distillation. The reaction conditions mentioned ensure that the endo/exo isomer is preferentially formed.
The novel procedure can be carried out either contin-ucausly or, in particular, discontinuously.
The endo/exo-8-N,N-dialkylamino-exo-tricyclo[5.2.1.0~~6]-decane is removed from the reaction mixture by simple distillation and is obtained by this procedure in such a pure form that no further purification is necessary for most intended uses.
The preparation of endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.026]decane by the novel process is illus-trated in more detail in the following examples. It is of course not intended to limit the invention to these specific embodiments.
Example 1: Preparation of endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.026]decane 2280 g (15 mol) of 8-hydroxy-tricyclo[5.2.1.026]decane and 228 g of a copper supported catalyst (RCH 60/35;
commercial product from Hoechst AG, Cu content about 60~
by weight, based on the catalyst composition) are initially introduced into a 4 1 three-necked flask provided with a stirrer, thermometer, water separator, reflux condenser and inlet tube, and are heated, while stirring. When a temperature of 100°C has been reached, 20 to 25 1/hour of hydrogen are continuously fed in via -5- ~ 2~oa~~5 the inlet tube to activate the catalyst, and 125 g/hour (2.78 mol) of dimethylamine in gaseous form are simul-taneously fed in via the same inlet tube.
Water is collected in the separator for the first time at a temperature of 14 8 to 150 °C . To accelerate the reac-tion, the temperature is adjusted to 170 to 175°C and the continuous addition of hydrogen and dimethylamine is continued. The water of reaction formed is constantly removed by the separator. After 6 hours, no further discharge of water is observed. 328 g of water of reac-tion are obtained in total, some of the excess dimethyl-amine being dissolved in it.
After cooling, the reaction product is filtered and analyzed by gas chromatography. The crude amine still contains 2 . 98 ~ of residual 8-hydroxy-tricyclo [ 5 . 2 .1. 026 ] -decane, which corresponds to a conversion of about 97~.
The selectivity for endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.026]decane is 80.8, and the ratio of endo to exo compound is 61 : 39.
Example 2 Example 1 is repeated, with the difference that the reaction temperature is 160 to 165°C. The water of reaction formed is again removed from the reaction mixture constantly by the water separator. After 6 hours, no further discharge of water is observed. 312 g of water of reaction are obtained in total, some of the excess dimethylamine being dissolved in this. The cooled and filtered crude amine still contains 3.75 of 8-hydroxy-tricyclo[5.2.1.02'6]decane, according to determination by gas chromatography, which corresponds to a conversion of about 96.2.
The selectivity for endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.0z~6]decane is 80.2, and the ratio of endo to exo compound is 81 : 19. 2 1 0 8 ~ ~ 5 Example 3 Example 1 is repeated, with the difference that the reaction temperature is 150 to 155°C. The water of reaction formed is again removed from the reaction mixture constantly by the separator. After 6 3/4 hours, no further discharge of water is observed. 284 g of water of reaction are obtained in total, some of the excess dimethylamine being dissolved in this. The cooled and filtered crude amine still contains 8.84 of 8-hydroxy-tricyclo[5.2.1.0z~6]decane according to analysis by gas chromatography, which corresponds to a conversion of about 91.28.
The selectivity of endo/exo-8-N,N-dimethylamino-exo-tricyclo[5.2.1.02'6]decane is 86.1$, and the ratio of endo to exo compound is 95 . 5.
Claims (11)
1. A process for preparing an endo/exo-8-N,N-dialkylamino-exo-tricyclo[5.2.1.0 2,6]decane, which process comprises reacting 8-hydroxytricyclo [5.2.1.0 2,6] decane with a secondary amine of the formula HNR1R2, in which R1 and R2 are identical or different and are in each case an alkyl radical having 1 to 6 carbon atoms, at 120 to 250°C in the presence of a hydrogenation catalyst and hydrogen, wherein the water formed during the reaction is removed continuously and the hydrogen is fed to the reaction mixture in an amount of 5 to 300 l/l of catalyst.
2. A process as claimed in claim 1, wherein R1 and R2 are an alkyl radical having 1 to 4 carbon atoms.
3. A process as claimed in claim 1, wherein R1 and R2 are an alkyl radical having 1 to 3 carbon atoms.
4. A process as claimed in claim 1 or 2, wherein dimethylamine is employed as the amine.
5. A process as claimed in claim 1 or 2, wherein the reaction is carried out at 145 to 195°C.
6. A process as claimed in claim 1 or 2, wherein a copper supported catalyst with a copper content of 15 to 85 %
by weight, based on the catalyst, is used as the hydrogenation catalyst.
by weight, based on the catalyst, is used as the hydrogenation catalyst.
7. A process as claimed in claim 1 or 2, wherein a copper supported catalyst with a copper content of 50 to 70 %
by weight, based on the catalyst, is used as the hydrogenation catalyst.
by weight, based on the catalyst, is used as the hydrogenation catalyst.
8. A process as claimed in claim 6, wherein the catalyst comprises kieselguhr or aluminum oxide as support material.
9. A process as claimed in claim 1 or 2, wherein 0.5 to 30 % by weight of catalyst, based on the hydroxy compound, is used.
10. A process as claimed in claim 1 or 2, wherein 3 to 20 % by weight of catalyst, based on the hydroxy compound, is used.
11. A process as claimed in claim 1 or 2, wherein hydrogen is fed continuously to the reaction mixture in an amount of 20 to 100 l/l of catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4232097A DE4232097A1 (en) | 1992-09-25 | 1992-09-25 | Process for the preparation of endo / exo-8-N, N-dialkylamino-exo-tricyclo [5.2.1.0 · 2 ·, · 6 ·] decane |
| DEP4232097.6 | 1992-09-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2106415A1 CA2106415A1 (en) | 1994-03-26 |
| CA2106415C true CA2106415C (en) | 1999-12-07 |
Family
ID=6468789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002106415A Expired - Fee Related CA2106415C (en) | 1992-09-25 | 1993-09-17 | Process for the preparation of endo/exo-8-n,n-dialkylamino-exo-tricyclo[5.2.1.0 2,6]decane |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0589341B1 (en) |
| JP (1) | JPH085846B2 (en) |
| AT (1) | ATE147064T1 (en) |
| CA (1) | CA2106415C (en) |
| DE (2) | DE4232097A1 (en) |
| ES (1) | ES2098611T3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2459299T3 (en) | 2008-09-19 | 2014-05-08 | Basf Se | Procedure for the continuous production of an amine with the use of an aluminum-copper catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE153639T1 (en) * | 1988-10-20 | 1997-06-15 | Chevron Usa Inc | NEW ZEOLITE SSZ-31 |
-
1992
- 1992-09-25 DE DE4232097A patent/DE4232097A1/en not_active Withdrawn
-
1993
- 1993-09-15 EP EP93114814A patent/EP0589341B1/en not_active Expired - Lifetime
- 1993-09-15 DE DE59304957T patent/DE59304957D1/en not_active Expired - Fee Related
- 1993-09-15 ES ES93114814T patent/ES2098611T3/en not_active Expired - Lifetime
- 1993-09-15 AT AT93114814T patent/ATE147064T1/en not_active IP Right Cessation
- 1993-09-16 JP JP5230439A patent/JPH085846B2/en not_active Expired - Lifetime
- 1993-09-17 CA CA002106415A patent/CA2106415C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06192185A (en) | 1994-07-12 |
| DE59304957D1 (en) | 1997-02-13 |
| EP0589341A1 (en) | 1994-03-30 |
| ATE147064T1 (en) | 1997-01-15 |
| CA2106415A1 (en) | 1994-03-26 |
| JPH085846B2 (en) | 1996-01-24 |
| ES2098611T3 (en) | 1997-05-01 |
| DE4232097A1 (en) | 1994-03-31 |
| EP0589341B1 (en) | 1997-01-02 |
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