METHOD OF MANUFACTURE OF OCTANEDIOIC ACID, PRECURSORS, AND DERIVATIVES

1 . A method for the manufacture of a dialkyl octenedioate having the formula (1)

wherein R is a C 1-18 alkyl,

the method comprising:

reacting gamma-valerolactone having the formula (2)

with an alcohol having the formula (3)

R—OH  (3)

in the presence of an acid or a base catalyst to provide an alkyl pentenoate having the formula (4)

and

converting the alkyl pentenoate having the formula (4) in the presence of a metathesis initiator to provide the dialkyl octenedioate having the formula (1),

wherein in formulas (3) and (4), R is a C 1-18 alkyl.

2 . The method of claim 1 , wherein the metathesis initiator is a transition metal carbene metathesis initiator, a transition metal salt in combination with an alkylating agent, and a transition metal complex capable of forming an active metal carbene by reaction with an olefin.

3 . The method of claim 1 , wherein converting the alkyl pentenoate having the formula (4) to the dialkyl octenedioate having the formula (1) comprises conducting the metathesis at a temperature of about −20° C. to about 600° C. and a pressure of about 0 to about 2000 psig.

4 . The method of claim 1 , further comprising converting levulinic acid or a levulinic ester having the formula (5)

wherein R 1 is a C 1-18 alkyl, to gamma-valerolactone having the formula (2).

5 . The method of claim 1 , further comprising converting angelica lactone having the formula (6)

to gamma-valerolactone having the formula (2).

6 . A method for the manufacture of oct-4-ene-1,8-dioic acid having the formula (7)

the method comprising:

reacting gamma-valerolactone having the formula (2)

with an alcohol having the formula (3)

ROH  (3)

in the presence of an acid or a base catalyst to provide an alkyl pentenoate having the formula (4)

wherein R is a C 1-18 alkyl;

hydrolyzing the alkyl pentenoate having the formula (4) to provide 4-pentenoic acid having the formula (8)

and

converting 4-pentenoic acid having the formula (8) in the presence of a metathesis catalyst to provide oct-4-ene-1,8-dioic acid having the formula (7).

7 . A method for the manufacture of oct-4-ene-1,8-dioic acid having the formula (7)

the method comprising:

preparing a dialkyl octenedioate having the formula (1)

according to claim 1 ; and

hydrolyzing the dialkyl octenedioate having the formula (1) to provide oct-4-ene-1,8-dioic acid having the formula (7).

8 . A method for the manufacture of 1,8-octanedioic acid having the formula (9)

the method comprising:

preparing a dialkyl octenedioate having the formula (1) according to claim 1

wherein R is C 1-18 alkyl;

converting the dialkyl octenedioate having the formula (1) to a dialkyl 1,8-octanedioate having the formula (10)

wherein R is a C 1-18 alkyl; and

hydrolyzing the dialkyl 1,8-octanedioate having the formula (10) to provide 1,8-octanedioic acid having the formula (9).

9 . A method for the manufacture of 1,8-octanedioic acid having the formula (9)

the method comprising:

preparing oct-4-ene-1,8-dioic acid having the formula (7) according to claim 6

and

converting oct-4-ene-1,8-dioic acid having the formula (7) to 1,8-octanedioic acid having the formula (9).

10 . A method for the manufacture of 1,8-octane diol having the formula (11)

the method comprising:

preparing a dialkyl octenedioate having the formula (1) according to claim 1

wherein R is a C 1-18 alkyl; and

converting the dialkyl octenedioate having the formula (1) to 1,8-octane diol having the formula (11).

11 . A method for the manufacture of 1,8-octane diol having the formula (11)

the method comprising:

preparing 1,8-octanedioic acid having the formula (9) according to claim 8

and

converting the 1,8-octanedioic acid having the formula (9) to 1,8-octane diol having the formula (11).

12 . A method for the manufacture of 1,6-dicyanohexane having the formula (12)

the method comprising:

preparing a dialkyl octenedioate having the formula (1) according to claim 1

wherein R is a C 1-18 alkyl;

reacting the dialkyl octenedioate having the formula (1) with hydrogen under hydrogenation conditions to provide a dialkyl 1,8-octanedioate having the formula (10)

wherein R is a C 1-18 alkyl; and

converting the dialkyl octanedioate having the formula (10) to 1,6-dicyanohexane having the formula (12).

13 . A method for the manufacture of 1,8-octane diamine having the formula (13)

the method comprising:

preparing 1,6-dicyanohexane having the formula (12) according to claim 12

and

reacting 1,6-dicyanohexane having the formula (12) with hydrogen in the presence of a nickel or cobalt catalyst to provide the 1,8-octane diamine having the formula (14).

14 . A method for the manufacture of 1,8-octane diamine having the formula (13)

the method comprising:

preparing 1,8-octanediol having the formula (11) according to claim 10

and

converting 1,8-octanediol having the formula (11) to 1,8-octane diamine having the formula (13).

15 . A method for the manufacture of 1,8-octane diisocyanate having the formula (14)

the method comprising:

preparing 1,8-octane diamine having the formula (13) according to claim 13

and

reacting the 1,8-octane diamine having the formula (13) with phosgene to provide the 1,8-octane diisocyanate having the formula (14).

16 . A method for the manufacture of a compound of the formula (15)

wherein R is C 1-18 alkyl, R 2 is H or C 1-18 alkyl,

the method comprising:

preparing a dialkyl octenedioate having the formula (1) according to claim 1

R is C 1-18 alkyl;

reacting the dialkyl octenedioate with carbon monoxide and hydrogen to provide a compound of the formula (16)

wherein R is C 1-18 alkyl; and

reacting the compound of the formula (16) with an amine of the formula (17)

R 2 —NH 2   (17)

wherein R 2 is H or C 1-18 alkyl, to provide the compound of formula (15).

17 . A method for the manufacture of a compound having the formula (18), a compound having the formula (19), or a combination comprising the compound having the formula (18) and the compound having the formula (19)

wherein in formulas (18) and (19), R is a C 1-18 alkyl; and R 2 is C 1-18 alkyl or H;

the method comprising:

preparing a compound having the formula (15) according to claim 16

wherein R is C 1-18 alkyl, R 2 is hydrogen or C 1-18 alkyl;

cyclizing the compound having the formula (15) to provide a mixture comprising the compound having the formula (18) and a compound having the formula (19); and

optionally separating the compound having the formula (18) from the compound having the formula (19).

18 . A method for the manufacture of a compound having the formula (34) and a compound having the formula (35), or a combination comprising the compound having the formula (34) and the compound having the formula (35)

the method comprising:

preparing a compound having the formula (15) according to claim 16

wherein R is a C 1-18 alkyl, R 2 is C 1-18 alkyl or hydrogen;

converting the compound having the formula (15) to an amino diacid having the formula (20)

cyclizing the amino diacid having the formula (20) to provide a mixture comprising the compound having the formula (34) and a compound having the formula (35); and

optionally separating the compound having the formula (34) from the compound having the formula (35).

19 . A method for the manufacture of a triisocyanate having the formula (21)

the method comprising:

preparing a dialkyl octenedioate having the formula (1) according to claim 1 ;

converting the dialkyl octenedioate having the formula (1) to a compound having the formula (16),

wherein R is C 1-18 alkyl;

converting the compound of the formula (16) to a triol having the formula (22)

converting the triol having the formula (22) to a triamine having the formula (23)

and

reacting the triamine having the formula (23) with phosgene to provide the triisocyanate of the formula (21).

20 . A method for the manufacture of a triester having the formula (24)

wherein R and R 3 are independently C 1-18 alkyl,

the method comprising:

preparing a dialkyl octenedioate having the formula (1) according to claim 1

R is C 1-18 alkyl; and

converting the dialkyl octenedioate having the formula (1) to the triester having the formula (24) in the presence of carbon monoxide, R 3 OH wherein R 3 is a C 1-18 alkyl, and a catalyst under carbonylation conditions.

21 .- 32 . (canceled)