Patent US4328644A successfully refreshed from Google Patents.
Patent US4927931A successfully refreshed from Google Patents.
US4927931A
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US
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Preparation of alkyl-extended, alcohol-extended or amine-extended piperazines
Assignee: Dow Chemical Co
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Filing: 1988-11-01
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Granted: 1990-05-22
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Expires: 2008-11-01
Abstract
Abstract A process for preparing alkyl-extended, alcohol-extended or amine-extended piperazines or mixtures thereof comprising contacting a difunctional aliphatic alcohol with a reactant amine, wherein at least one of the aliphatic alcohol or the reactant amine contains a piperazine moiety, in the presence of a catalyst containing a Group VB metal oxide or a Group VB metal phosphate, or mixtures thereof. For example, monoethanolamine reacts with piperazine in the presence of a catalyst of niobic acid supported on hydrated alumina to yield predominantly N-(2-aminoethyl)piperazine. Also, N-hydroxyethylpiperazine reacts with piperazine in the presence of a catalyst of niobium phosphate to yield predominantly 1,2-bis(piperazinyl)ethane.
Inventors
- 👤 David C. Molzahn
- 👤 George E. Hartwell
- 👤 Robert G. Bowman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 17:45
CPC Classifications
C; C07; C07D; C07D295/00; C07D295/02; C07D295/023; C07D295/04; C07D295/08; C07D295/084; C07D295/088; C07D295/12; C07D295/125; C07D295/13
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
70 words
A process for preparing alkyl-extended, alcohol-extended or amine-extended piperazines or mixtures thereof comprising contacting an aliphatic alcohol with a reactant amine, wherein at least one of the aliphatic alcohol or reactant amine contains a piperazine moiety, the contacting occurring in the presence of a catalyst under conditions such that an alkyl-extended, alcohol-extended or amine-extended piperazine or mixture thereof is formed, said catalyst being a composition containing a Group VB metal.
Claim 2
Dependent Claim
70 words
A process for preparing alkyl-extended, alcohol-extended or amine-extended piperazines or mixtures thereof comprising contacting an aliphatic alcohol with a reactant amine, wherein at least one of the aliphatic alcohol or reactant amine contains a piperazine moiety, the contacting occurring in the presence of a catalyst under conditions such that an alkyl-extended, alcohol-extended or amine-extended piperazine or mixture thereof is formed, said catalyst being a composition containing a Group VB metal.
Claim 3
Dependent Claim
24 words
The process of claim 1 wherein the catalyst composition is a Group VB metal oxide or a Group VB metal phosphate or mixture thereof.
Claim 4
Dependent Claim
91 words
The process of claim 1 wherein the aliphatic alcohol is represented by the formula: ##STR6## wherein A is H, OH or NHR; each B is independently NR or O; each R is independently hydrogen, hydroxyl, amino, an alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a monocyclic aromatic moiety: x is an integer from 2 to about 12; k is an integer from 0 to about 150; and z is an integer from 0 to about 12.
Claim 5
Dependent Claim
10 words
The process of claim 3 wherein each R is hydrogen.
Claim 6
Dependent Claim
13 words
The process of claim 4 wherein x is 2 and z is 1.
Claim 7
Dependent Claim
27 words
The process of claim 5 wherein each R is hydrogen, A is NH 2 , k is 0, z is 1, and the aliphatic alcohol is monoethanolamine.
Claim 8
Dependent Claim
87 words
The process of claim 1 wherein the aliphatic alcohol is represented by the formula: ##STR7## wherein each B is independently NR or O; each R is independently hydrogen, hydroxy, amino, an alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a monocyclic aromatic moiety; each y is independently an integer from 0 to about 12; j is an integer from 1 to about 6; and n is an integer from 0 to about 6.
Claim 9
Dependent Claim
26 words
The process of claim 7 wherein each R is H, y is 1, j is 1 and n is 0, and the aliphatic alcohol is N-(2-hydroxyethyl)piperazine.
Claim 10
Dependent Claim
78 words
The process of claim 1 wherein the reactant amine is represented by the formula: ##STR8## wherein each B is independently NR or O; each R is independently hydrogen, hydroxy, amino, an alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a monocyclic aromatic moiety; each x is independently an integer from 2 to about 12; and k is an integer from 0 to about 150.
Claim 11
Dependent Claim
12 words
The process of claim 9 wherein the reactant amine is an ethylenepolyamine.
Claim 12
Dependent Claim
82 words
The process of claim 1 wherein the reactant amine is represented by the formula: ##STR9## wherein each R is independently hydrogen, hydroxy, amino, an alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a monocyclic aromatic moiety: each y is independently an integer from 0 to about 12; each 1 is independently an integer from 0 to about 6; and j is an integer from 1 to about 6.
Claim 13
Dependent Claim
25 words
The process of claim 11 wherein each R is hydrogen, y is 0, j is 1, each 1 is 0, and the compound is piperazine.
Claim 14
Dependent Claim
20 words
The process of claim 1 wherein the mole ratio of reactant amine to aliphatic alcohol is at least about 1.
Claim 15
Dependent Claim
12 words
The process of claim 2 wherein the Group VB metal is niobium.
Claim 16
Dependent Claim
12 words
The process of claim 14 wherein the catalyst is a niobium phosphate.
Claim 17
Dependent Claim
19 words
The process of claim 15 wherein the phosphorus to niobium metal mole ratio is no greater than about 1.0.
Claim 18
Dependent Claim
12 words
The process of claim 16 wherein the catalyst is NbOPO 4 .
Claim 19
Dependent Claim
16 words
The process of claim 14 wherein the catalyst is an oxide or hydrated oxide of niobium.
Claim 20
Dependent Claim
15 words
The process of claim 18 wherein the catalyst is niobic acid supported on hydrated alumina.
Claim 21
Dependent Claim
31 words
The process of claim 1 wherein the amount of catalyst is in the range from about 0.1 weight percent to about 20 weight percent based on the weight of reactant amine.
Claim 22
Dependent Claim
20 words
The process of claim 1 wherein the temperature is in the range from about 200° C. to about 350° C.
Claim 23
Dependent Claim
19 words
The process of claim 1 wherein the pressure is in the range from about atmospheric to about 4000 psig.
Claim 24
Dependent Claim
32 words
The process of claim 1 wherein the liquid hourly space velocity is in the range from about 0.1 g ml -1 hr -1 to about 10.0 g ml -1 hr -1 .
Claim 25
Dependent Claim
91 words
The process of claim 1 wherein the alcohol-extended and amine-extended piperazines are represented by the formula: ##STR10## wherein each B is independently O or NR; each R is independently hydrogen, hydroxy, amino, an alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a monocyclic aromatic moiety; each y is independently an integer from 0 to about 12; h and h' are independently integers from 0 to about 6; and j' is an integer from 0 to about 6.
Claim 26
Dependent Claim
28 words
The process of claim 24 wherein B is NR, R is hydrogen, y is 2, h is 1, j' and h' are 0, and the product is N-(2-aminoethyl)piperazine.
Claim 27
Dependent Claim
39 words
A process for preparing N-(2-aminoethyl)piperazine comprising contacting monoethanolamine with piperazine in the presence of a catalyst containing niobium oxide supported on boehmite alumina under conditions sufficient to prepare N-(2-aminoethyl)piperazine in a selectivity of at least about 20 weight percent
Claim 28
Dependent Claim
39 words
A process for preparing N-(2-aminoethyl)piperazine comprising contacting monoethanolamine with piperazine in the presence of a catalyst containing niobium oxide supported on boehmite alumina under conditions sufficient to prepare N-(2-aminoethyl)piperazine in a selectivity of at least about 20 weight percent
Claim 29
Dependent Claim
20 words
The process of claim 26 wherein the N-(2-aminoethyl)piperazine is produced in a selectivity of at least about 30 weight percent.
Claim 30
Dependent Claim
20 words
The process of claim 27 wherein the N-(2-aminoethyl)piperazine is produced in a selectivity of at least about 40 weight percent.
Claim 31
Dependent Claim
35 words
A process for preparing 1,2-bis(piperazinylethane) comprising contacting hydroxyethylpiperazine with piperazine in the presence of a catalyst containing niobium phosphate under conditions sufficient to prepare 1,2-bis(piperazinyl)ethane in a selectivity of at least about 40 weight percent.
Claim 32
Dependent Claim
35 words
A process for preparing 1,2-bis(piperazinylethane) comprising contacting hydroxyethylpiperazine with piperazine in the presence of a catalyst containing niobium phosphate under conditions sufficient to prepare 1,2-bis(piperazinyl)ethane in a selectivity of at least about 40 weight percent.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1993-05-21 | 1993-11-20 | 1994-05-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1997-05-21 | 1997-11-20 | 1998-05-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2001-05-21 | 2001-11-20 | 2002-05-22 | $7700.00 | Window Closed / Lapsed |