US4983735A — Preparation of alcohol-extended and amine-extende…

Claim 1

Independent Claim 98 words

A process for preparing alcohol-extended and amine-extended piperazines comprising contacting a difunctional aliphatic alcohol with a reactant amine, the difunctional alcohol having at least one hydroxyl moiety bound to a primary carbon atom and at least one additional moiety selected from the group consisting of hydroxyl, primary amine and secondary amine functionalities, and wherein at least one of the difunctional alcohol or reactant amine contains a piperazine moiety, the contacting occurring in the presence of a catalyst under reaction conditions such that a mixture of alcohol-extended and/or amine-extended piperazines is formed, said catalyst containing a tungsten heteropoly acid.

Claim 2

Dependent Claim 98 words

A process for preparing alcohol-extended and amine-extended piperazines comprising contacting a difunctional aliphatic alcohol with a reactant amine, the difunctional alcohol having at least one hydroxyl moiety bound to a primary carbon atom and at least one additional moiety selected from the group consisting of hydroxyl, primary amine and secondary amine functionalities, and wherein at least one of the difunctional alcohol or reactant amine contains a piperazine moiety, the contacting occurring in the presence of a catalyst under reaction conditions such that a mixture of alcohol-extended and/or amine-extended piperazines is formed, said catalyst containing a tungsten heteropoly acid.

Claim 3

Dependent Claim 92 words

The process of claim 1 wherein the difunctional alcohol is represented by the formula ##STR6## wherein A is OH or NHR; each B is independently NR or O; each R is independently hydrogen, hydroxy, amino, a lower alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a phenyl or tolyl 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 1 to about 12.

Claim 4

Dependent Claim 9 words

The process of claim 2 wherein R is hydrogen.

Claim 5

Dependent Claim 13 words

The process of claim 3 wherein x is 2 and z is 1.

Claim 6

Dependent Claim 26 words

The process of claim 4 wherein R is hydrogen, A is NH 2 , k is 0, z is 1, and the difunctional alcohol is monoethanolamine.

Claim 7

Dependent Claim 89 words

The process of claim 1 wherein the difunctional alcohol is represented by the formula: ##STR7## wherein each B is independently NR or O; each R is independently hydrogen, hydroxy, amino, a lower alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a phenyl or tolyl 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 8

Dependent Claim 25 words

The process of claim 6 wherein R is H, y is 1, j is 1 and n is 0, and the difunctional alcohol is N-(2-hydroxyethyl)piperazine.

Claim 9

Dependent Claim 80 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, a lower alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a phenyl or tolyl moiety; each x is independently an integer from 2 to about 12; and k is an integer from 0 to about 150.

Claim 10

Dependent Claim 12 words

The process of claim 8 wherein the reactant amine is an ethylenepolyamine.

Claim 11

Dependent Claim 84 words

The process of claim 1 wherein the reactant amine is represented by the formula: ##STR9## wherein each R is independently hydrogen, hydroxy, amino, a lower alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a phenyl or tolyl 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 12

Dependent Claim 24 words

The process of claim 10 wherein R is hydrogen, y is 0, j is 1, each l is 0, and the compound is piperazine.

Claim 13

Dependent Claim 21 words

The process of claim 1 wherein the mole ratio of reactant amine to difunctional aliphatic alcohol is at least about 1.

Claim 14

Dependent Claim 151 words

The process of claim 1 wherein the catalyst is represented by the formula C c [D d W w M m O o ] wherein C is the counter cation, D is the heteroatom selected from the group consisting of the elements of Groups IIIA, IVA, VA, VIA, the transition elements and the rare earth lanthanide and actinide metals of the Periodic Table, W is tungsten, M is an additional framework atom selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, Mn, Fe, Co, Ni, and Cu, and O is oxygen, and wherein d is an integer from 1 to 3, w is an integer from about 8 to about 40, m is an integer from 0 to 2, and o is an integer from about 20 to about 100, and c is a number sufficient to maintain overall charge neutrality by balancing the charge of the anion.

Claim 15

Dependent Claim 12 words

The process of claim 13 wherein the heteroatom is P or Si.

Claim 16

Dependent Claim 13 words

The process of claim 14 wherein the heteropoly acid is a 12-tungstophosphoric acid.

Claim 17

Dependent Claim 17 words

The process of claim 15 wherein the heteropoly acid is H 3 [PW 12 O 40 ].

Claim 18

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 19

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 20

Dependent Claim 19 words

The process of claim 1 wherein the pressure is in the range from about atmospheric to about 4000 psig.

Claim 21

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 22

Dependent Claim 93 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, a lower alkyl moiety of C 1 -C 12 carbon atoms, a hydroxyalkyl or aminoalkyl moiety of C 1 -C 12 carbon atoms, or a phenyl or tolyl 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 23

Dependent Claim 28 words

The process of claim 21 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 24

Dependent Claim 36 words

A process for preparing N-(2-aminoethyl)piperazine comprising contacting monoethanolamine with piperazine in the presence of a catalyst containing titania-supported 12-tungstophosphoric acid under conditions sufficient to prepare N-(2-aminoethyl)piperazine in a selectivity of at least about 30 weight percent.

Claim 25

Dependent Claim 36 words

A process for preparing N-(2-aminoethyl)piperazine comprising contacting monoethanolamine with piperazine in the presence of a catalyst containing titania-supported 12-tungstophosphoric acid under conditions sufficient to prepare N-(2-aminoethyl)piperazine in a selectivity of at least about 30 weight percent.

Claim 26

Dependent Claim 20 words

The process of claim 23 wherein the N-(2-aminoethyl)piperazine is produced in a selectivity of at least about 50 weight percent.

Claim 27

Dependent Claim 20 words

The process of claim 24 wherein the N-(2-aminoethyl)piperazine is produced in a selectivity of at least about 60 weight percent.

Claim 28

Dependent Claim 92 words

A process for preparing alcohol-extended and amine-extended piperazines comprising contacting a difunctional aliphatic alcohol with a reactant amine, wherein the difunctional aliphatic alcohol is selected from the group consisting of polyols, alkanolamines, polyether amino alcohols, and hydroxyalkyl-substituted piperazines, and wherein at least one of the difunctional alcohol or the reactant amine contains a piperazine moiety, the contacting occurring in the presence of a catalytic amount of a tungsten heteropoly acid wherein the heteroatom is P or Si and under reaction conditions such that a mixture of alcohol-extended and/or amine-extended piperazines is formed.

Claim 29

Dependent Claim 92 words

A process for preparing alcohol-extended and amine-extended piperazines comprising contacting a difunctional aliphatic alcohol with a reactant amine, wherein the difunctional aliphatic alcohol is selected from the group consisting of polyols, alkanolamines, polyether amino alcohols, and hydroxyalkyl-substituted piperazines, and wherein at least one of the difunctional alcohol or the reactant amine contains a piperazine moiety, the contacting occurring in the presence of a catalytic amount of a tungsten heteropoly acid wherein the heteroatom is P or Si and under reaction conditions such that a mixture of alcohol-extended and/or amine-extended piperazines is formed.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1994-01-07	1994-07-09	1995-01-08	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1998-01-07	1998-07-09	1999-01-08	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2002-01-07	2002-07-09	2003-01-08	$7700.00	Window Closed / Lapsed

Preparation of alcohol-extended and amine-extended piperazines

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