Synthesis of cyclic organic compounds and metallocenes

Patent metadata

Field	Value
Publication number	US-11059840-B2
Application number	US-201816649929-A
Country	US
Kind code	B2
Filing date	Sep 19, 2018
Priority date	Sep 28, 2017
Publication date	Jul 13, 2021
Grant date	Jul 13, 2021

Abstract

A method comprising synthesizing a cyclic organic compound via reaction of an unsubstituted or substituted cyclohexene with an unsubstituted or substituted acrylic acid in the presence of phosphoric and/or sulfonic acid reagent to make the cyclic organic compound. Also, a method of synthesizing a ligand for a transition metal, and a related substituted ligand-metal complex and catalyst, from the unsubstituted or substituted cyclohexene and unsubstituted or substituted acrylic acid. Also, the cyclic organic compound, ligand, and substituted ligand-metal complex and catalyst synthesized thereby. Also a method of polymerizing an olefin with the catalyst to give a polyolefin, and the polyolefin made thereby.

First claim

The invention claimed is:

1. A method of synthesizing a zirconocene dichloride complex of formula (8):

(“compound (8)”) and/or its R5/R4 regioisomer, the method comprising synthesizing the compound (8) and/or its R5/R4 regioisomer according to steps (A) to (E):
(A) contacting a compound of formula (1) (“compound (1)”):

wherein R1, R2, R3, and R3a are independently H or (C 1 -C 4 )alkyl, or any two adjacent R1 to R3a groups are bonded together to form a (C 1 -C 4 )alkylene and each of the remaining groups of R1 to R3a independently is H or (C 1 -C 4 )alkyl, with a compound of formula (2) (“compound (2)”):

wherein R4 is H or (C 1 -C 4 )alkyl, in the presence of an effective amount of a phosphoric and/or sulfonic acid reagent and under reaction conditions sufficient to make a compound of formula (3) (“compound (3)”):

and/or its oxo/R4 regioisomer; wherein R1 to R4 are as defined above; and with the proviso that when each of R1 to R3a is H and R4 is methyl, the phosphoric and/or sulfonic acid reagent and contacting step (A) are free of a polyphosphoric acid (PPA);
(B) contacting the compound (3) and/or its oxo/R4 regioisomer with either a hydride-functional reducing agent or a (C 1 -C 4 )alkyl lithium, under reaction conditions sufficient to make a compound of formula (4) (“compound (4)”):

and/or its (HO,R5)/R4 regioisomer, respectively, wherein R1 to R4 are as defined above and R5 is either H or (C 1 -C 4 )alkyl, respectively; and
(C) contacting the compound (4) and/or its (HO,R5)/R4 regioisomer with dehydration reaction conditions to make a compound of formula (5) (“compound (5)”):

and/or its R5/R4 regioisomer, respectively; wherein R1 to R5 are as defined above;
(D) contacting the compound (5) and/or its R5/R4 regioisomer with an alkyl lithium under reaction conditions sufficient to make a compound of formula (6) (“compound (6)”):

and/or its R5/R4 regioisomer, wherein R1 to R5 are as defined above; and
(E) contacting the compound (6) and/or its R5/R4 regioisomer with a compound of formula (7) (“compound (7)”):

under reaction conditions sufficient to make the compound (8) and/or its R5/R4 regioisomer, wherein R1 to R5 are as defined above and each of R6 to R10 is independently H or (C 1 -C 4 )alkyl.

2. The method of claim 1 further comprising synthesizing a zirconocene dimethyl complex of formula (9):

(“compound (9)”) and/or its R5/R4 regioisomer, the method comprising synthesizing the compound (8) and/or its R5/R4 regioisomer according to steps (A) to (E) of claim 1 ; and (F) contacting the compound (8) and/or its R5/R4 regioisomer with an effective amount of methyl magnesium bromide under reaction conditions sufficient to make the compound (9) and/or its R5/R4 regioisomer, wherein R1 to R10 are as defined in claim 1 .

3. The method of claim 1 , wherein the phosphoric and/or sulfonic acid reagent is a polyphosphoric acid (PPA); a mixture of a phosphorous pentoxide and methanesulfonic acid (“P 2 O 5 /H 3 CSO 3 H mixture”), or a reaction product of the P 2 O 5 /H 3 CSO 3 H mixture; or a combination of a PPA and a P 2 O 5 /H 3 CSO 3 H mixture, or a reaction product of the PPA and the P 2 O 5 /H 3 CSO 3 H mixture; with the proviso that when each of R1 to R3a is H and R4 is methyl, the phosphoric and/or sulfonic acid reagent and the contacting step (A) are free of the PPA.

4. The method of claim 1 wherein the phosphoric and/or sulfonic acid reagent is a polyphosphoric acid (PPA); with the proviso that at least one of R1 to R3a is (C 1 -C 4 )alkyl or R4 is H.

5. The method of claim 1 , wherein the phosphoric and/or sulfonic acid reagent is the P 2 O 5 /H 3 CSO 3 H mixture, or a reaction product of the P 2 O 5 /H 3 CSO 3 H mixture.

6. The method of claim 1 , wherein the phosphoric and/or sulfonic acid reagent is the combination of the PPA and the P 2 O 5 /H 3 CSO 3 H mixture, or a reaction product of the PPA and the P 2 O 5 /H 3 CSO 3 H mixture.

7. The method of claim 1 , characterized by any one of limitations (i) to (ix): (i) wherein at least one of R1 to R3a is a (C 1 -C 4 )alkyl or R4 is H; (ii) wherein each of R1 to R4 is H; (iii) wherein each of R1 to R3a is H and R4 is methyl; (iv) wherein in compound (1) each of R1, R2, and R3a is H and R3 is methyl; in compound (2) R4 is methyl; and in compound (3) each of R1, R2, and R3a is H and each of R3 and R4 is methyl; and in its oxo/R4 regioisomer each of R1, R2, and R3 is H and each of R3a and R4 is each methyl; (v) wherein R1 and/or R2 is methyl and R3 and R3a is H; (vi) wherein R1 is methyl, R2 is 1-methylethyl (i.e., isopropyl), and R3 and R3a are H; (vii) wherein R1 is 1-methylethyl (i.e., isopropyl), R2 is methyl, and R3 and R3a are H; (viii) wherein R1 and R2 independently are (C 1 -C 4 )alkyl, R3 and R3a are H, and the stereochemistry of the carbon atom bonded to R1 is (R) and the stereochemistry to the carbon atom bonded to R2 is (S); and (ix) wherein R1 and R2 independently are (C 1 -C 4 )alkyl, R3 and R3a are H, and the stereochemistry of the carbon atom bonded to R1 is (S) and the stereochemistry to the carbon atom bonded to R2 is (R).

8. The method of claim 2 further comprising polymerizing an olefin, the method comprising contacting ethylene and/or an alpha-olefin with a catalyst made by contacting the compound (8) or (9), or its R5/R4 regioisomer, made by the method of claim 2 , with an activator, under conditions sufficient to make a polyolefin polymer comprising a polyethylene homopolymer, an ethylene/alpha-olefin copolymer, or a poly(alpha-olefin) homopolymer.

9. The method of claim 1 wherein the compound (4) or its (HO,R5)/R4 regioisomer is free of platinum, palladium, nickel, rhodium, and ruthenium.

Assignees

• Univation Tech Llc

Inventors

• Padilla-Acevedo Angela I
• Kuhlman Roger L

Classifications

• C07C2602/08

  the other ring being five-membered, e.g. indane · CPC title

• C07C29/40

  with compounds containing carbon-to-metal bonds · CPC title

• C07F17/00 Primary

  Metallocenes · CPC title

• C07C45/455

  with carboxylic acids or their derivatives · CPC title

• C08F10/02 Primary

  Ethene · CPC title