WO2019166782A1 - Catalysts - Google Patents
Catalysts Download PDFInfo
- Publication number
- WO2019166782A1 WO2019166782A1 PCT/GB2019/050489 GB2019050489W WO2019166782A1 WO 2019166782 A1 WO2019166782 A1 WO 2019166782A1 GB 2019050489 W GB2019050489 W GB 2019050489W WO 2019166782 A1 WO2019166782 A1 WO 2019166782A1
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- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- aryl
- compound
- halo
- alkoxy
- Prior art date
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- 239000003054 catalyst Substances 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 121
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 203
- 125000003118 aryl group Chemical group 0.000 claims description 124
- 125000005843 halogen group Chemical group 0.000 claims description 109
- 125000003545 alkoxy group Chemical group 0.000 claims description 101
- 229910003827 NRaRb Inorganic materials 0.000 claims description 83
- 125000003342 alkenyl group Chemical group 0.000 claims description 68
- 125000000304 alkynyl group Chemical group 0.000 claims description 68
- 125000004104 aryloxy group Chemical group 0.000 claims description 60
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- 239000001257 hydrogen Substances 0.000 claims description 49
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 49
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 37
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 18
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 claims description 10
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000010936 titanium Chemical group 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000003950 cyclic amides Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- VNEACLJMGRLSEJ-UHFFFAOYSA-N CC1=C(C)C2=C(C)C(C)=C(C)C2=C1C Chemical group CC1=C(C)C2=C(C)C(C)=C(C)C2=C1C VNEACLJMGRLSEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 17
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- -1 Poly(lactic acids) Polymers 0.000 description 9
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 CC(*)(N*)[N+]* Chemical compound CC(*)(N*)[N+]* 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910007928 ZrCl2 Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010068 TiCl2 Inorganic materials 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical compound [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000003389 potentiating effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YSJHFYXOBVZFDU-UHFFFAOYSA-N CC(C1C)C(C)C2C1C(C)C(C)C2C Chemical compound CC(C1C)C(C)C2C1C(C)C(C)C2C YSJHFYXOBVZFDU-UHFFFAOYSA-N 0.000 description 1
- VJRYJFUOBFAHGH-UHFFFAOYSA-N CC1C(C)C2C(C)=C(C)C(C)C2C1C Chemical compound CC1C(C)C2C(C)=C(C)C(C)C2C1C VJRYJFUOBFAHGH-UHFFFAOYSA-N 0.000 description 1
- YBGCOFSXTRUWOR-UHFFFAOYSA-N [Th]CC1=CC=CC=C1 Chemical compound [Th]CC1=CC=CC=C1 YBGCOFSXTRUWOR-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000599 controlled substance Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
Definitions
- the present invention relates to new catalytic compounds. More specifically, the present invention relates to catalytic compounds suitable for use in the polymerisation of cyclic esters and/or cyclic amides.
- PLAs Poly(lactic acids)
- PLAs Poly(lactic acids)
- PLAs are both biodegradable and biocompatible, they are of equal value to the field of medicine, wherein their versatile physical properties make them suitable for in vivo applications (e.g. as media for controlled drug delivery devices).
- (m-nC) or "(m-nC) group” used alone or as a prefix, refers to any group having m to n carbon atoms.
- alkyl refers to straight or branched chain alkyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. In particular, an alkyl may have 1 , 2, 3 or 4 carbon atoms.
- alkenyl refers to straight or branched chain alkenyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms.
- This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl and hexenyl, as well as both the cis and trans isomers thereof.
- alkynyl refers to straight or branched chain alkynyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms.
- the term includes reference to alkynyl moieties containing 1 , 2 or 3 carbon-carbon triple bonds (CoC). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl and hexynyl.
- haloalkyl refers to alkyl groups being substituted with one or more halogens (e.g. F, Cl, Br or I). This term includes reference to groups such as 2-fluoropropyl, 3-chloropentyl, as well as perfluoroalkyl groups, such as perfluoromethyl.
- alkoxy refers to -O-alkyl, wherein alkyl is straight or branched chain and comprises 1 , 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1 , 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
- aryl or“aromatic” as used herein means an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms.
- Aryl is often phenyl but may be a polycyclic ring system, having two or more rings, at least one of which is aromatic. This term includes reference to groups such as phenyl, naphthyl and the like. Unless otherwise specification, aryl groups may be substituted by one or more substituents. A particularly suitable aryl group is phenyl.
- aryloxy refers to -O-aryl, wherein aryl has any of the definitions discussed herein. Also encompassed by this term are aryloxy groups in having an alkylene chain situated between the O and aryl groups.
- halogen or“halo” as used herein refers to F, Cl, Br or I. In a particular, halogen may be F or Cl, of which Cl is more common.
- substituted as used herein in reference to a moiety means that one or more, especially up to 5, more especially 1 , 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents.
- optionally substituted as used herein means substituted or unsubstituted.
- cyclic esters and“cyclic amides” as used herein refer to heterocycles containing at least one ester or amide moiety. It will be understood that lactides, lactones and lactams are encompassed by these terms.
- the first aspect of the invention provides a compound having a structure according to formula (I) shown below:
- X is selected from zirconium or hafnium; Y is selected from:
- halo hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NR a R b , - NR a R b , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NR a R b , aryl, (1- 6C)alkoxy, -C(0)NR a R b , and Si[(1-4C)alkyl] 3 , or
- each R x is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1-3C)fluoroalkyl, aryl and aryloxy, and
- R y is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1-3C)fluoroalkyl, aryl and aryloxy;
- each R 1 is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1- 3C)fluoroalkyl, aryl and aryloxy; and
- R 2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1- 3C)fluoroalkyl, aryl and aryloxy;
- R a and R b are independently hydrogen or (1-4C)alkyl.
- the new compounds which contain a permethylpentalene (“Pn*”) ligands and an amidinate ligand, are particularly active in the polymerisation of lactides and lactones (e.g. e-caprolactone).
- the compound of formula (I) may exist as a dimer. It will be understood that such dimeric forms of the compound of formula (I) are within the scope of the present invention. Dimeric forms of the compound of formula (I) may adopt the general structure:
- X is zirconium
- X may also be titanium.
- each R 1 group is independently selected from (1-6C)alkyl, (2- 4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1-3C)fluoroalkyl, aryl and aryloxy.
- each R 1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2- 4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
- each R 1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1- 6C)alkoxy, aryl and aryloxy.
- each R 1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
- each R 1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with 1-3 groups selected from halo, (1-4C)alkyl and (1- 2C)alkoxy.
- each R 1 group is independently selected from methyl, ethyl, isopropyl and tertbutyl, or each R 1 group is independently a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl.
- Both R 1 groups are suitably identical to one another.
- R 2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
- R 2 is selected from hydrogen, (1-6C)alkyl, -N'Pr'Pr and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)fluoroalkyl, aryl and aryloxy.
- R 2 is selected from hydrogen, (1-4C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, aryl and aryloxy.
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1- 4C)alkyl.
- R a and R b are independently selected from methyl, ethyl, iso-propyl and tert-butyl.
- R a and R b are independently selected from methyl, ethyl and iso-propyl.
- R a and R b are identical.
- Y is i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NR a R b , -NR a R b , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NR a R b , aryl, (1-6C)alkoxy, -C(0)NR a R b , and Si[(1-4C)alkyl] 3 , or iii) a ligand having a structure according to formula A, wherein each R x has any of the definitions discussed hereinbefore in relation to R 1 , and R y has any of the definitions discussed hereinbefore in relation to R 2 .
- Y is
- halo hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NR a R , -NR a R , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NR a R b , aryl, (1-6C)alkoxy, -C(0)NR a R b , and Si[(1-4C)alkyl] 3 , or iii) a ligand having a structure according to formula A, wherein both R 1 groups are identical, each R x is identical to R 1 , and R y is identical to R 2 .
- Y is
- halo or ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, -NR a R b , aryl, (1- 6C)alkoxy, -C(0)NR a R , and Si[(1-4C)alkyl] 3 .
- halo or ii) (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, aryl and (1-6C)alkoxy.
- halo or ii) (1-4C)alkyl, (1-4C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
- Y is
- Y is
- the compound of formula (I) has a structure according to formula (la) shown below:
- X, Y and R 2 have any of the definitions discussed hereinbefore in respect of formula (I); each R 3 is independently selected from (1-4C)alkyl and (1-3C)fluoroalkyl; and each n is independently 0,1 , 2 or 3.
- the compound of formula (I) has a structure according to formula (la), wherein
- X, Y and R 2 have any of the definitions discussed hereinbefore in respect of formula (I);
- each R 3 is independently an ortho or para substituent selected from (1-4C)alkyl and (1- 3C)fluoroalkyl;
- each n is independently 0, 1 , 2 or 3.
- the compound of formula (I) has a structure according to formula (la), wherein
- X is zirconium
- R 2 is selected from hydrogen, (1-6C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy
- Y is: i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NR a R b , -NR a R b , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NR a R b , aryl, (1-6C)alkoxy, -C(0)NR a R b , and Si[(1-4C)alkyl] 3 , or iii) an amidinate ligand identical to that depicted in formula (la) (i.e. that comprising groups R 1 and R 2 ); each R 3 is independently an ortho or para substituent selected from (1-4C)alkyl and (1- 3C)fluoroalkyl; and
- each n is independently 0, 1 , 2 or 3.
- the compound of formula (I) has a structure according to formula (la), wherein
- X is zirconium
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl;
- Y is: i) halo, or ii) (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, aryl and (1-6C)alkoxy; each R 3 is independently an ortho or para substituent selected from (1-4C)alkyl and (1- 3C)fluoroalkyl; and
- each n is independently 0, 1 , 2 or 3.
- the compound of formula (I) has a structure according to formula (la), wherein
- X is zirconium
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl;
- Y is: i) chloro, or ii) (1-4C)alkoxy or a phenoxy group that is optionally substituted with 1 or 2 (1-4C)alkyl groups; each R 3 is independently an ortho or para substituent selected from methyl, iso-propyl and trifluoromethyl; and
- each n is independently 0, 1 , 2 or 3.
- the compound of formula (I) has a structure according to formula (lb) shown below:
- X, Y and R 2 have any of the definitions discussed hereinbefore in respect of formula (I).
- the compound of formula (I) has a structure according to formula (lb), wherein X is zirconium;
- R 2 is selected from hydrogen, (1-6C)alkyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)fluoroalkyl, aryl and aryloxy;
- Y is: i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NR a R b , -NR a R b , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NR a R b , aryl, (1-6C)alkoxy, -C(0)NR a R b , and Si[(1-4C)alkyl] 3 , or iii) an amidinate ligand identical to that depicted in formula (la) (i.e. that comprising groups R 1 and R 2 ).
- the compound of formula (I) has a structure according to formula (lb), wherein
- X is zirconium
- R 2 is selected from hydrogen, (1-4C)alkyl, -N'PHPr and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy and (1- 3C)fluoroalkyl;
- Y is: i) halo, or ii) (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, aryl and (1-6C)alkoxy.
- the compound of formula (I) has a structure according to formula (lb), wherein
- X is zirconium
- R 2 is selected from hydrogen, (1-4C)alkyl, -N'PHPr and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy and trifluoromethyl;
- Y is: i) chloro, or ii) (1-4C)alkoxy or a phenoxy group that is optionally substituted with 1 or 2 (1-4C)alkyl groups.
- the compound of formula (I) has a structure according to formula (lc) shown below:
- X, R 1 and R 2 have any of the definitions discussed hereinbefore in respect of formula (I).
- the compound of formula (I) has a structure according to formula (lc) wherein
- X is zirconium
- each R 1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy; and
- R 2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
- the compound of formula (I) has a structure according to formula (lc) wherein
- X is zirconium
- each R 1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)haloalkyl, aryl and aryloxy; and R 2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -N'Pr'Pr and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
- the compound of formula (I) has a structure according to formula (lc) wherein
- X is zirconium
- each R 1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy; and
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
- the compound of formula (I) has a structure according to formula (lc) wherein
- X is zirconium
- R 1 group is selected from methyl, ethyl, isopropyl and tertbutyl, or R 1 group is a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl; and
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
- the compound of formula (I) has a structure according to formula (Id) shown below:
- R 4 is selected from (1-4C)alkyl and aryl, either or which is optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-3C)fluoroalkyl.
- the compound of formula (I) has a structure according to formula (Id) wherein
- X is zirconium
- each R 1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy;
- R 2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy; and
- R 4 is selected from (1-4C)alkyl and phenyl, either or which is optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-3C)fluoroalkyl.
- the compound of formula (I) has a structure according to formula (Id) wherein
- X is zirconium
- each R 1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)haloalkyl, aryl and aryloxy; and
- R 2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -N'Pr'Pr and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
- the compound of formula (I) has a structure according to formula (Id) wherein
- X is zirconium
- each R 1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy;
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy; and R 4 is selected from methyl, iso-propyl, tert-butyl and phenyl, either or which is optionally substituted with one or more substituents selected from methyl, iso-propyl, tert-butyl and trifluoromethyl.
- the compound of formula (I) has a structure according to formula (Id) wherein
- X is zirconium
- R 1 group is selected from methyl, ethyl, isopropyl and tertbutyl, or R 1 group is a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl;
- R 2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl;
- R 4 is selected from tert-butyl, 2,6-dimethyl phenyl and 2,6-diisopropyl phenyl.
- the compound of formula (I) has any of the following structures:
- the compound of formula (I) has any of the following structures:
- the compound of formula (I) has any of the following structures:
- the compound of formula (I) has any of the following structures:
- the compound of formula (I) is immobilised on a solid support material. Supporting the compound on such a solid support allows the resulting material to be used in slurry phase (as opposed to solution phase) catalysis. Suitable solid support materials will be familiar to one of ordinary skill in the art.
- the compound of formula (I) may be supported directly or indirectly (e.g. by a linking moiety) on the solid support material. It will be understood that the compound of formula (I) may undergo one or more minor structure modifications (e.g. loss of the group Y) as a consequence of having been immobilised on a solid support material. Such minor structural modifications are within the scope of the invention.
- the compounds of formula (I) may be synthesised by any suitable process known in the art. Particular examples of processes for the preparation of the compounds are set out in the accompanying examples.
- the compounds of formula (I) are prepared according to a process comprising the steps of:
- X is as defined in formula (I)
- M is a metal (such as Li, Na or K) and Q is halo (e.g. chloro);
- R 1 and R 2 are as defined in formula (I) and M + is a metal cation (such as Li + , Na + or K + ); and optionally thereafter
- Y is as defined in formula (I) and M is a metal (such as Li, Na or K).
- step b) is typically implemented.
- M is Li in step a).
- Any suitable solvent may be used for steps a) and b) of the process defined above.
- a particularly suitable solvent may be, for example, diethyl ether, toluene, THF, dichloromethane, chloroform, hexane DMF, benzene etc.
- step a) the compound of formula (III) is typically added dropwise to the compound of formula (II) in order to prevent double ligand substitution (unless this is desired).
- reaction conditions e.g. temperature, pressures, reaction times, agitation etc.
- X is selected from zirconium, hafnium and titanium;
- Y is selected from:
- halo hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NR a R b , - NR a R b , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NR a R b , aryl, (1- 6C)alkoxy, -C(0)NR a R b , and Si[(1-4C)alkyl] 3 , or
- each R x is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1-3C)fluoroalkyl, aryl and aryloxy, and
- R y is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1-3C)fluoroalkyl, aryl and aryloxy;
- each R 1 is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1- 3C)fluoroalkyl, aryl and aryloxy; and R 2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a
- R a and R b are independently hydrogen or (1-4C)alkyl.
- the compound of statement 1 wherein X is zirconium.
- each R 1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NR a R b , (1-6C)alkoxy, -C(0)NR a R b , (1-3C)fluoroalkyl, aryl and aryloxy.
- each R 1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
- each R 1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy.
- each R 1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
- each R 1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with 1-3 groups selected from halo, (1-4C)alkyl and (1-2C)alkoxy.
- each R 1 group is independently selected from methyl, ethyl, isopropyl and tertbutyl, or each R 1 group is independently a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl.
- R 1 groups are identical
- R 2 is selected from hydrogen, (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NR a R b and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
- R 2 is selected from hydrogen, (1- 6C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy.
- R 2 is selected from hydrogen, (1- 4C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, aryl and aryloxy.
- R 2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
- R 2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
- R 2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
- the compound of any preceding statement, wherein the group -(R 1 )N-CH(R 2 )-N(R 1 )- is an amidinate ligand having any one of the following structures:
- X, Y and R 2 are as defined in any preceding statement; each R 3 is independently selected from (1-4C)alkyl and (1-3C)fluoroalkyl; and each n is independently 0, 1 , 2 or 3.
- R 4 is selected from (1-4C)alkyl and aryl, either or which is optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-3C)fluoroalkyl.
- the compound of statement 1 wherein the compound has any of the following structures:
- Fig. 1 shows the 1 H NMR spectrum of Pn * Zr(CI)(HC(N-2,6-'Pr-C 6 H 3 ) 2 ) recorded at 298 K in CD2CI2. * denotes NMR solvent residue.
- Fig. 2 shows the molecular structure of Pn * Zr(CI)(HC(N-2,6-'Pr-C 6 H 3 ) 2 ), shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
- Fig. 3 shows the 1 H NMR spectrum of Pn * Zr(CI)(MeC(N'Pr)2) recorded at 298 K in Ob ⁇ d . * denotes NMR solvent residue.
- Fig. 4 shows the molecular structure of dimeric [Pn * Zr(CI)(MeC(N'Pr)2)]2, shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
- Fig. 5 shows the 1 H NMR spectrum of Pn * Zr(CI)(PhC(N'Pr)2) recorded at 298 K in Ob ⁇ d . * denotes NMR solvent residue and residual THF.
- Fig. 6 shows the molecular structure of Pn * Zr(CI)(PhC(N'Pr)2), shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
- An additional symmetry inequivalent molecule composes the asymmetric unit and is also omitted for clarity.
- Fig. 7 shows the 1 H NMR spectrum of Pn * Zr(CI)(HC(N-4-Me-C6H4)2) recorded at 298 K in CD2CI2. *denotes NMR solvent residue and residual hexane.
- Fig. 8 shows the molecular structure of dimeric [Pn * Zr(CI)(HC(N-4-Me-C 6 H 4 ) 2 )] 2 , shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
- Fig. 9 shows the 1 H NMR spectrum of Pn * Zr(0-2,6-Me-C 6 H 3 )(PhC(N'Pr) 2 ) recorded at 298 K in O d ⁇ d . *denotes NMR solvent residue.
- Fig. 10 shows the molecular structure of Pn * Zr(0-2,6-Me-C 6 H 3 )(PhC(N'Pr) 2 ), shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
- An additional symmetry inequivalent molecule composes the asymmetric unit and is also omitted for clarity.
- Fig. 11 is a plot showing conversion of L-lactide to Polylactide as a function of time using the compounds of Example 1. Reactions catalysed by the series of permethylpentalene zirconium catalysts. Polymerisations were performed in a 0.5M L-lactide solution in Ob ⁇ d at 80 °C with 2 mol% [Zr]
- Fig. 12 is a plot showing concentration of e-caprolactone monomer as a function of polymerisation time using Pn * Zr(0-2,6-Me-C 6 H 3 )(PhC(N'Pr) 2 ), with the reaction following a zero order rate law. Polymerisations were performed in a 0.5M e-caprolactone solution in Ob ⁇ d at room temperature with 2 mol% Pn * Zr(0-2,6-Me-C6H 3 )(PhC(N'Pr) 2 ).
- Fig. 13 shows the 1 H NMR spectrum of Pn*Zr ⁇ ('PrN) 2 C(4-OMe-C 6 H 4 ) ⁇ CI recorded at 298K in O d ⁇ d . *denotes NMR solvent residue and # denotes residual thf.
- Fig. 14 shows the 1 H NMR spectrum of Pn*Zr ⁇ ('PrN) 2 C(4-CF 3 -C 6 H 4 ) ⁇ CI recorded at 298K in Ob ⁇ d . *denotes NMR solvent residue and # denotes residual thf.
- Fig. 15 shows the 1 H NMR spectrum of Pn*Ti ⁇ (2,6-'PrC 6 H 3 N) 2 CH ⁇ CI recorded at 298K in Ob ⁇ d . *denotes NMR solvent residue.
- Fig. 16 shows the 1 H NMR spectrum of Pn*Ti ⁇ ('PrN)2C(C6H5) ⁇ CI recorded at 298K in CeD 6 . *denotes NMR solvent residue and # denotes residual pentane.
- [0084] [Pn*ZrCl2]2LiCI THF x (0.114 mmol) and a metal salt of the desired ligand (M-L*, 0.229 mmol) were combined as solids in a Schlenk tube and toluene (3 ml_) was added at room temperature.
- Fig. 1 shows the 1 H NMR spectrum of Pn * Zr(CI)(HC(N-2,6-'Pr-C 6 H 3 ) 2 ) recorded at 298 K in CD2CI2.
- the molecular structure is depicted in Fig. 2.
- Fig. 3 shows the 1 H NMR spectrum of Pn * Zr(CI)(MeC(N'Pr)2) recorded at 298 K in CeD 6 .
- the molecular dimeric structure is depicted in Fig. 4.
- Fig. 5 shows the 1 H NMR spectrum of Pn * Zr(CI)(PhC(N'Pr)2) recorded at 298 K in CeD 6 .
- the molecular structure is depicted in Fig. 6.
- Fig. 7 shows the 1 H NMR spectrum of Pn * Zr(CI)(HC(N-4-Me-C 6 H 4 ) 2 ) recorded at 298 K in CD2CI2.
- the molecular dimeric structure is depicted in Fig. 8. 1.3. Procedure for the synthesis of Pn * Zr(Q-2,6-Me-C6H3)(PhC(N l Pr) 2 )
- Fig. 9 shows the 1 H NMR spectrum of Pn*Zr(0-2,6-Me-C 6 H 3 )(PhC(N'Pr) 2 ) recorded at 298 K in C 6 D 6 .
- the molecular structure is depicted in Fig. 10.
- Fig. 11 shows that all of the Example 1 compounds are potent catalysts for L-lactide polymerisation.
- Fig. 12 shows that Pn*Zr(0-2,6-Me-C 6 H 3 )(PhC(N'Pr) 2 ) is a potent catalyst for e- caprolactone polymerisation.
- Rh*T ⁇ (2,6-'RGq 6 H 3 N) 2 qH ⁇ OI was synthesised by reaction of 1 eq. [Pn*TiCl2]2 with 2 eq. K ⁇ (2,6-'PrC 6 H 3 N) 2 CH ⁇ in a NMR tube.
- the 1 H NMR spectrum is shown in Fig. 15.
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Abstract
Catalytic compounds suitable for use in the polymerisation of cyclic esters and/or cyclic amides are described. The catalytic compounds are based on Group IV metals bound to permethylpentalene and amidinate ligands.
Description
CATALYSTS
INTRODUCTION
[0001] The present invention relates to new catalytic compounds. More specifically, the present invention relates to catalytic compounds suitable for use in the polymerisation of cyclic esters and/or cyclic amides.
BACKGROUND OF THE INVENTION
[0002] Poly(lactic acids) (PLAs) have been studied intensively over the past few decades due to the promise they have shown as potential alternatives to petroleum-based polymers for uses a plastics, fibres and coatings. Moreover, since PLAs are both biodegradable and biocompatible, they are of equal value to the field of medicine, wherein their versatile physical properties make them suitable for in vivo applications (e.g. as media for controlled drug delivery devices).
[0003] Lactic acid forms PLA upon polycondensation. However, the fact that this reaction is in equilibrium, and the difficulties in completely removing water, makes it difficult to obtain PLAs of high molecular weight. With this in mind, ring opening polymerisation (ROP) of lactides is the most efficient route to PLAs with controlled molecular weights and narrow molecular weight distributions.
[0004] Metal complexes useful for initiating ring opening polymerisation of lactides are known.
[0005] Wenshan Ren et al, Inorganic Chemistry Communications, 30, (2013), 26-28 report that benzyl thorium metallocenes [q5-1 ,3-(Me3C)2C5H3]2 Th(CH2Ph)2 (1) and [q5-1 ,2,4-(Me3C)3C5H2]2 Th(CH2Ph)2 (2) can initiate the ring opening polymerisation of racemic-lactide (rac-LA) under mild conditions. Complete conversion of 500 equiv of lactide occurs within 5h at 40°C in dichloromethane at [rac-LA]=1.0 mol L 1 , and the molecular weight distribution is very narrow (ca.1.15) over the entire monomer-to-initiator range, indicating a single-site catalyst system.
[0006] Yalan Ning et al, Organometallics 2008, 27, 5632-5640 report four neutral zirconocene bis(ester enolate) and non-zirconocene bis(alkoxy) complexes employed for ring-opening polymerisations and chain transfer polymerisations of L-lactide ( -LA) and e-caprolactone (e-CL).
[0007] In spite of the above, due to the high value that industry places on such materials, there remains a need for catalysts/initiators capable of effectively polymerising cyclic esters (such as lactides and lactones) and cyclic amides.
The present invention was devised with the foregoing in mind.
SUMMARY OF THE INVENTION
[0008] According to a first aspect of the present invention there is provided a compound having a structural formula according to formula (I) defined herein.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0009] The term "(m-nC)" or "(m-nC) group" used alone or as a prefix, refers to any group having m to n carbon atoms.
[0010] The term“alkyl” as used herein refers to straight or branched chain alkyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. This term includes reference to groups such as methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n-butyl, sec-butyl or tert-butyl), pentyl, hexyl and the like. In particular, an alkyl may have 1 , 2, 3 or 4 carbon atoms.
[0011] The term“alkenyl” as used herein refers to straight or branched chain alkenyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkenyl moieties containing 1 , 2 or 3 carbon-carbon double bonds (C=C). This term includes reference to groups such as ethenyl (vinyl), propenyl (allyl), butenyl, pentenyl and hexenyl, as well as both the cis and trans isomers thereof.
[0012] The term“alkynyl” as used herein refers to straight or branched chain alkynyl moieties, typically having 1 , 2, 3, 4, 5 or 6 carbon atoms. The term includes reference to alkynyl moieties containing 1 , 2 or 3 carbon-carbon triple bonds (CºC). This term includes reference to groups such as ethynyl, propynyl, butynyl, pentynyl and hexynyl.
[0013] The term“haloalkyl” as used herein refers to alkyl groups being substituted with one or more halogens (e.g. F, Cl, Br or I). This term includes reference to groups such as 2-fluoropropyl, 3-chloropentyl, as well as perfluoroalkyl groups, such as perfluoromethyl.
[0014] The term“alkoxy” as used herein refers to -O-alkyl, wherein alkyl is straight or branched chain and comprises 1 , 2, 3, 4, 5 or 6 carbon atoms. In one class of embodiments, alkoxy has 1 , 2, 3 or 4 carbon atoms. This term includes reference to groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentoxy, hexoxy and the like.
[0015] The term "aryl" or“aromatic” as used herein means an aromatic ring system comprising 6, 7, 8, 9 or 10 ring carbon atoms. Aryl is often phenyl but may be a polycyclic ring system, having two or more rings, at least one of which is aromatic. This term includes reference to
groups such as phenyl, naphthyl and the like. Unless otherwise specification, aryl groups may be substituted by one or more substituents. A particularly suitable aryl group is phenyl.
[0016] The term“aryloxy” as used herein refers to -O-aryl, wherein aryl has any of the definitions discussed herein. Also encompassed by this term are aryloxy groups in having an alkylene chain situated between the O and aryl groups.
[0017] The term "halogen" or“halo” as used herein refers to F, Cl, Br or I. In a particular, halogen may be F or Cl, of which Cl is more common.
[0018] The term“substituted” as used herein in reference to a moiety means that one or more, especially up to 5, more especially 1 , 2 or 3, of the hydrogen atoms in said moiety are replaced independently of each other by the corresponding number of the described substituents. The term“optionally substituted” as used herein means substituted or unsubstituted.
[0019] It will, of course, be understood that substituents are only at positions where they are chemically possible, the person skilled in the art being able to decide (either experimentally or theoretically) without inappropriate effort whether a particular substitution is possible.
The terms“cyclic esters” and“cyclic amides” as used herein refer to heterocycles containing at least one ester or amide moiety. It will be understood that lactides, lactones and lactams are encompassed by these terms.
Compounds of the invention
[0020] As discussed above, the first aspect of the invention provides a compound having a structure according to formula (I) shown below:
X is selected from zirconium or hafnium;
Y is selected from:
i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, - NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NRaRb, aryl, (1- 6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or
iii) a ligand having a structure according to formula A below:
A wherein
each Rx is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy, and
Ry is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy;
each R1 is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1- 3C)fluoroalkyl, aryl and aryloxy; and
R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1- 3C)fluoroalkyl, aryl and aryloxy;
and wherein Ra and Rb are independently hydrogen or (1-4C)alkyl.
[0021] Through intensive investigations, the inventors have developed new compounds that exhibit activity in catalysing the polymerisation of cyclic ester and cyclic amides. The new compounds, which contain a permethylpentalene (“Pn*”) ligands and an amidinate ligand, are particularly active in the polymerisation of lactides and lactones (e.g. e-caprolactone).
[0022] It will be appreciated that the compounds of formula (I) exist in a number of isomeric forms. For example, the exact nature of the bonding between metal X and the amidinate ligand may give rise to various isomeric forms, as illustrated below:
[0023] It will be appreciated that, depending on the nature of ligand Y, the compound of formula (I) may exist as a dimer. It will be understood that such dimeric forms of the compound of formula (I) are within the scope of the present invention. Dimeric forms of the compound of formula (I) may adopt the general structure:
[0024] Most suitably, X is zirconium.
[0025] In embodiments of first aspect of the invention, X may also be titanium.
[0026] In an embodiment, each R1 group is independently selected from (1-6C)alkyl, (2- 4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups
selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy.
[0027] Suitably, each R1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2- 4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
[0028] More suitably, each R1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1- 6C)alkoxy, aryl and aryloxy.
[0029] Even more suitably, each R1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
[0030] Yet more suitably, each R1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with 1-3 groups selected from halo, (1-4C)alkyl and (1- 2C)alkoxy.
[0031] In a particularly suitable embodiment, each R1 group is independently selected from methyl, ethyl, isopropyl and tertbutyl, or each R1 group is independently a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl.
[0032] Both R1 groups are suitably identical to one another.
[0033] In an embodiment, R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
[0034] Suitably, R2 is selected from hydrogen, (1-6C)alkyl, -N'Pr'Pr and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)fluoroalkyl, aryl and aryloxy.
[0035] More suitably, R2 is selected from hydrogen, (1-4C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, aryl and aryloxy.
[0036] Even more suitably, R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
[0037] Yet more suitably, R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
[0038] In a particularly suitable embodiment, R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1- 4C)alkyl.
[0039] In an embodiment, Ra and Rb are independently selected from methyl, ethyl, iso-propyl and tert-butyl.
[0040] Suitably, Ra and Rb are independently selected from methyl, ethyl and iso-propyl.
[0041] More suitably, Ra and Rb are identical.
[0042] When taken in combination with the group -N-C(R2)H-N-, the groups R1 and R2 form an amidinate ligand -(R1)N-C(R2)H-N(R1)-. Exemplary amidinate ligands useful in the context of the present invention are as follows:
[0043] In an embodiment, Y is
i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, -NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or iii) a ligand having a structure according to formula A, wherein each Rx has any of the definitions discussed hereinbefore in relation to R1, and Ry has any of the definitions discussed hereinbefore in relation to R2.
[0044] Suitably, Y is
i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaR , -NRaR , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or iii) a ligand having a structure according to formula A, wherein both R1 groups are identical, each Rx is identical to R1 , and Ry is identical to R2.
[0045] More suitably, Y is
i) halo, or ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, -NRaRb, aryl, (1- 6C)alkoxy, -C(0)NRaR , and Si[(1-4C)alkyl]3.
[0046] Even more suitably, Y is
i) halo, or ii) (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, aryl and (1-6C)alkoxy.
[0047] Yet more suitably, Y is
i) halo, or ii) (1-4C)alkyl, (1-4C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
[0048] Yet even more suitably, Y is
i) chloro or bromo, or
ii) (1-4C)alkoxy, phenyl and phenoxy, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
[0049] In a particularly suitable embodiment, Y is
i) chloro, or ii) (1-4C)alkoxy, phenyl and phenoxy, any of which is optionally substituted with 1-3 groups selected from halo and (1-4C)alkyl.
[0050] In another particularly suitable embodiment, Y is
i) chloro, or ii) (1-4C)alkoxy (e.g. f-butoxy) or a phenoxy group that is optionally substituted (e.g. at the ortho position) with 1 or 2 (1-4C)alkyl groups (e.g. methyl or isopropyl).
[0051] In an embodiment, the compound of formula (I) has a structure according to formula (la) shown below:
wherein
X, Y and R2 have any of the definitions discussed hereinbefore in respect of formula (I); each R3 is independently selected from (1-4C)alkyl and (1-3C)fluoroalkyl; and each n is independently 0,1 , 2 or 3.
[0052] Suitably, the compound of formula (I) has a structure according to formula (la), wherein
X, Y and R2 have any of the definitions discussed hereinbefore in respect of formula (I);
each R3 is independently an ortho or para substituent selected from (1-4C)alkyl and (1- 3C)fluoroalkyl; and
each n is independently 0, 1 , 2 or 3.
[0053] More suitably, the compound of formula (I) has a structure according to formula (la), wherein
X is zirconium;
R2 is selected from hydrogen, (1-6C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy
Y is: i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, -NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or iii) an amidinate ligand identical to that depicted in formula (la) (i.e. that comprising groups R1 and R2); each R3 is independently an ortho or para substituent selected from (1-4C)alkyl and (1- 3C)fluoroalkyl; and
each n is independently 0, 1 , 2 or 3.
[0054] Even more suitably, the compound of formula (I) has a structure according to formula (la), wherein
X is zirconium;
R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl;
Y is: i) halo, or ii) (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, aryl and (1-6C)alkoxy;
each R3 is independently an ortho or para substituent selected from (1-4C)alkyl and (1- 3C)fluoroalkyl; and
each n is independently 0, 1 , 2 or 3.
[0055] Yet more suitably, the compound of formula (I) has a structure according to formula (la), wherein
X is zirconium;
R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl;
Y is: i) chloro, or ii) (1-4C)alkoxy or a phenoxy group that is optionally substituted with 1 or 2 (1-4C)alkyl groups; each R3 is independently an ortho or para substituent selected from methyl, iso-propyl and trifluoromethyl; and
each n is independently 0, 1 , 2 or 3.
[0056] In an embodiment, the compound of formula (I) has a structure according to formula (lb) shown below:
wherein
X, Y and R2 have any of the definitions discussed hereinbefore in respect of formula (I).
[0057] Suitably, the compound of formula (I) has a structure according to formula (lb), wherein
X is zirconium;
R2 is selected from hydrogen, (1-6C)alkyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)fluoroalkyl, aryl and aryloxy;
Y is: i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, -NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1- 4C)alkyl, nitro, -NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or iii) an amidinate ligand identical to that depicted in formula (la) (i.e. that comprising groups R1 and R2).
[0058] More suitably, the compound of formula (I) has a structure according to formula (lb), wherein
X is zirconium;
R2 is selected from hydrogen, (1-4C)alkyl, -N'PHPr and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy and (1- 3C)fluoroalkyl;
Y is: i) halo, or ii) (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, aryl and (1-6C)alkoxy.
[0059] Even more suitably, the compound of formula (I) has a structure according to formula (lb), wherein
X is zirconium;
R2 is selected from hydrogen, (1-4C)alkyl, -N'PHPr and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy and trifluoromethyl;
Y is: i) chloro, or
ii) (1-4C)alkoxy or a phenoxy group that is optionally substituted with 1 or 2 (1-4C)alkyl groups.
[0060] In an embodiment, the compound of formula (I) has a structure according to formula (lc) shown below:
wherein
X, R1 and R2 have any of the definitions discussed hereinbefore in respect of formula (I).
[0061] In an embodiment, the compound of formula (I) has a structure according to formula (lc) wherein
X is zirconium;
each R1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy; and
R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
[0062] In an embodiment, the compound of formula (I) has a structure according to formula (lc) wherein
X is zirconium;
each R1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)haloalkyl, aryl and aryloxy; and
R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -N'Pr'Pr and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
[0063] In an embodiment, the compound of formula (I) has a structure according to formula (lc) wherein
X is zirconium;
each R1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy; and
R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
[0064] In an embodiment, the compound of formula (I) has a structure according to formula (lc) wherein
X is zirconium;
R1 group is selected from methyl, ethyl, isopropyl and tertbutyl, or R1 group is a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl; and
R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
[0065] In an embodiment, the compound of formula (I) has a structure according to formula (Id) shown below:
wherein
X, R1 and R2 have any of the definitions discussed hereinbefore in respect of formula (I); and
R4 is selected from (1-4C)alkyl and aryl, either or which is optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-3C)fluoroalkyl.
[0066] In an embodiment, the compound of formula (I) has a structure according to formula (Id) wherein
X is zirconium;
each R1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy;
R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy; and
R4 is selected from (1-4C)alkyl and phenyl, either or which is optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-3C)fluoroalkyl.
[0067] In an embodiment, the compound of formula (I) has a structure according to formula (Id) wherein
X is zirconium;
each R1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, (1- 3C)haloalkyl, aryl and aryloxy; and
R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -N'Pr'Pr and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2- 6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
[0068] In an embodiment, the compound of formula (I) has a structure according to formula (Id) wherein
X is zirconium;
each R1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy;
R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy; and
R4 is selected from methyl, iso-propyl, tert-butyl and phenyl, either or which is optionally substituted with one or more substituents selected from methyl, iso-propyl, tert-butyl and trifluoromethyl.
[0069] In an embodiment, the compound of formula (I) has a structure according to formula (Id) wherein
X is zirconium;
R1 group is selected from methyl, ethyl, isopropyl and tertbutyl, or R1 group is a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl;
R2 is selected from hydrogen, (1-4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl; and
R4 is selected from tert-butyl, 2,6-dimethyl phenyl and 2,6-diisopropyl phenyl.
[0070] In an embodiment, the compound of formula (I) has any of the following structures:
[0071] In an embodiment, the compound of formula (I) has any of the following structures:
[0072] Suitably, the compound of formula (I) has any of the following structures:
[0073] In an embodiment, the compound of formula (I) has any of the following structures:
[0074] In an embodiment, the compound of formula (I) is immobilised on a solid support material. Supporting the compound on such a solid support allows the resulting material to be used in slurry phase (as opposed to solution phase) catalysis. Suitable solid support materials will be familiar to one of ordinary skill in the art. The compound of formula (I) may be supported directly or indirectly (e.g. by a linking moiety) on the solid support material. It will be understood that the compound of formula (I) may undergo one or more minor structure modifications (e.g. loss of the group Y) as a consequence of having been immobilised on a solid support material. Such minor structural modifications are within the scope of the invention.
Synthesis
[0075] The compounds of formula (I) may be synthesised by any suitable process known in the art. Particular examples of processes for the preparation of the compounds are set out in the accompanying examples.
[0076] Suitably, the compounds of formula (I) are prepared according to a process comprising the steps of:
a) reacting a compound of formula (II) shown below:
wherein X is as defined in formula (I), M is a metal (such as Li, Na or K) and Q is halo (e.g. chloro);
with a compound of formula (III) shown below:
wherein R1 and R2 are as defined in formula (I) and M+ is a metal cation (such as Li+, Na+ or K+); and optionally thereafter
b) reacting the resulting product with a compound of formula (IV) shown below:
M(Y)
(IV)
wherein Y is as defined in formula (I) and M is a metal (such as Li, Na or K).
[0077] If a compound of formula (I) is required in which Y is other than halo, then step b) is typically implemented.
[0078] Suitably, M is Li in step a).
[0079] Any suitable solvent may be used for steps a) and b) of the process defined above. A particularly suitable solvent may be, for example, diethyl ether, toluene, THF, dichloromethane, chloroform, hexane DMF, benzene etc.
[0080] Within step a), the compound of formula (III) is typically added dropwise to the compound of formula (II) in order to prevent double ligand substitution (unless this is desired).
[0081] A person of skill in the art will be able to select suitable reaction conditions (e.g. temperature, pressures, reaction times, agitation etc.) for such a synthesis.
[0082] The following numbered statements 1 to 33 are not claims, but instead serve to define particular aspects and embodiments of the claimed invention:
1. A compound having a structure according to formula I shown below:
X is selected from zirconium, hafnium and titanium;
Y is selected from:
i) halo, hydrogen, a phosphonate, sulfonate or borate anion, ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, - NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NRaRb, aryl, (1- 6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or
iii) a ligand having a structure according to formula A below:
A wherein
each Rx is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy, and
Ry is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy;
each R1 is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1- 3C)fluoroalkyl, aryl and aryloxy; and
R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1- 3C)fluoroalkyl, aryl and aryloxy;
and wherein Ra and Rb are independently hydrogen or (1-4C)alkyl. The compound of statement 1 , wherein X is zirconium. The compound of statement 1 or 2, wherein each R1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy. The compound of any one of statements 1 , 2 or 3, wherein each R1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy. The compound of any preceding statement, wherein each R1 group is independently selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy. The compound of any preceding statement, wherein each R1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy. The compound of any preceding statement, wherein each R1 group is independently selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with 1-3 groups selected from halo, (1-4C)alkyl and (1-2C)alkoxy. The compound of any preceding statement, wherein each R1 group is independently selected from methyl, ethyl, isopropyl and tertbutyl, or each R1 group is independently a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl. The compound of any preceding statement, wherein both R1 groups are identical
The compound of any preceding statement, wherein R2 is selected from hydrogen, (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy. The compound of any preceding statement, wherein R2 is selected from hydrogen, (1- 6C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy. The compound of any preceding statement, wherein R2 is selected from hydrogen, (1- 4C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, aryl and aryloxy. The compound of any preceding statement, wherein R2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy. The compound of any preceding statement, wherein R2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl. The compound of any preceding statement, wherein R2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl. The compound of any preceding statement, wherein the group -(R1)N-CH(R2)-N(R1)- is an amidinate ligand having any one of the following structures:
i) halo, hydrogen, a phosphonate, sulfonate or borate anion,
ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, -NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or iii) a ligand having a structure according to formula A, wherein each Rx has any of the definitions appearing in any preceding statement in relation to R1, and Ry has any of the definitions appearing in any preceding statement in relation to R2. The compound of any preceding statement, wherein Y is
i) halo, hydrogen, a phosphonate, sulfonate or borate anion,
ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaR , -NRaR , aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or
iii) a ligand having a structure according to formula A, wherein each Rx is identical to R1 , and Ry is identical to R2. The compound of any preceding statement, wherein Y is
i) halo, or
ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, - NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3. The compound of any preceding statement, wherein Y is
i) halo, or
ii) (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, aryl and (1-6C)alkoxy. The compound of any preceding statement, wherein Y is
i) halo, or
ii) (1-4C)alkyl, (1-4C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl. The compound of any preceding statement, wherein Y is
i) chloro or bromo, or
ii) (1-4C)alkoxy, phenyl and phenoxy, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl. The compound of any preceding statement, wherein Y is
i) chloro, or
ii) (1-4C)alkoxy, phenyl and phenoxy, any of which is optionally substituted with 1-3 groups selected from halo and (1-4C)alkyl. The compound of any preceding statement, wherein Y is
i) chloro, or
ii) (1-4C)alkoxy or a phenoxy group that is optionally substituted with 1 or 2 (1-4C)alkyl groups. The compound of any preceding statement, wherein the compound of formula (I) has a structure according to formula (la) shown below:
X, Y and R2 are as defined in any preceding statement; each R3 is independently selected from (1-4C)alkyl and (1-3C)fluoroalkyl; and each n is independently 0, 1 , 2 or 3. The compound of any one of statements 1 to 24, wherein the compound of formula (I) has a structure according to formula (lb) shown below:
X, Y and R2 are as defined in any preceding statement;
The compound of any one of statements 1 to 24, wherein the compound of formula (I) has a structure according to formula (lc) shown below:
X, R1 and R2 are as defined in any preceding statement. The compound of any one of statements 1 to 24, wherein the compound of formula (I) has a structure according to formula (Id) shown below:
X, R1 and R2 are as defined in any preceding statement; and
R4 is selected from (1-4C)alkyl and aryl, either or which is optionally substituted with one or more substituents selected from (1-4C)alkyl and (1-3C)fluoroalkyl. The compound of statement 1 , wherein the compound has any of the following structures:
The compound of statement 1, wherein the compound has any of the following structures:
31. The compound of statement 1, wherein the compound has any of the following structures:
WO 2019/166782 PCT/GB2019/050489
31
32. The compound of statement 1 , wherein the compound has any of the following
structures:
33. The compound of any preceding statement, wherein the compound of formula (I) is
immobilised on a solid support material.
EXAMPLES
[0083] Examples of the invention will now be described, for the purpose of illustration only, with reference to the accompanying figures, in which:
Fig. 1 shows the 1H NMR spectrum of Pn*Zr(CI)(HC(N-2,6-'Pr-C6H3)2) recorded at 298 K in CD2CI2. *denotes NMR solvent residue.
Fig. 2 shows the molecular structure of Pn*Zr(CI)(HC(N-2,6-'Pr-C6H3)2), shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
Fig. 3 shows the 1 H NMR spectrum of Pn*Zr(CI)(MeC(N'Pr)2) recorded at 298 K in Obϋd. *denotes NMR solvent residue.
Fig. 4 shows the molecular structure of dimeric [Pn*Zr(CI)(MeC(N'Pr)2)]2, shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
Fig. 5 shows the 1 H NMR spectrum of Pn*Zr(CI)(PhC(N'Pr)2) recorded at 298 K in Obϋd. *denotes NMR solvent residue and residual THF.
Fig. 6 shows the molecular structure of Pn*Zr(CI)(PhC(N'Pr)2), shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity. An additional symmetry inequivalent molecule composes the asymmetric unit and is also omitted for clarity.
Fig. 7 shows the 1 H NMR spectrum of Pn*Zr(CI)(HC(N-4-Me-C6H4)2) recorded at 298 K in CD2CI2. *denotes NMR solvent residue and residual hexane.
Fig. 8 shows the molecular structure of dimeric [Pn*Zr(CI)(HC(N-4-Me-C6H4)2)]2, shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity.
Fig. 9 shows the 1 H NMR spectrum of Pn*Zr(0-2,6-Me-C6H3)(PhC(N'Pr)2) recorded at 298 K in Odϋd. *denotes NMR solvent residue.
Fig. 10 shows the molecular structure of Pn*Zr(0-2,6-Me-C6H3)(PhC(N'Pr)2), shown with thermal ellipsoids at 50% probability and hydrogen atoms removed for clarity. An additional symmetry inequivalent molecule composes the asymmetric unit and is also omitted for clarity.
Fig. 11 is a plot showing conversion of L-lactide to Polylactide as a function of time using the compounds of Example 1. Reactions catalysed by the series of permethylpentalene zirconium catalysts. Polymerisations were performed in a 0.5M L-lactide solution in Obϋd at 80 °C with 2 mol% [Zr]
Fig. 12 is a plot showing concentration of e-caprolactone monomer as a function of polymerisation time using Pn*Zr(0-2,6-Me-C6H3)(PhC(N'Pr)2), with the reaction following a zero order rate law. Polymerisations were performed in a 0.5M e-caprolactone solution in Obϋd at room temperature with 2 mol% Pn*Zr(0-2,6-Me-C6H3)(PhC(N'Pr)2).
Fig. 13 shows the 1 H NMR spectrum of Pn*Zr{('PrN)2C(4-OMe-C6H4)}CI recorded at 298K in Odϋd. *denotes NMR solvent residue and # denotes residual thf.
Fig. 14 shows the 1 H NMR spectrum of Pn*Zr{('PrN)2C(4-CF3-C6H4)}CI recorded at 298K in Obϋd. *denotes NMR solvent residue and # denotes residual thf.
Fig. 15 shows the 1 H NMR spectrum of Pn*Ti{(2,6-'PrC6H3N)2CH}CI recorded at 298K in Obϋd. *denotes NMR solvent residue.
Fig. 16 shows the 1H NMR spectrum of Pn*Ti{('PrN)2C(C6H5)}CI recorded at 298K in CeD6. *denotes NMR solvent residue and # denotes residual pentane.
Example 1 - Synthesis of compounds
1.1. General procedure for the synthesis of Pn*Zr(CI)L (L = and
PhC(N'Pr)?
[0084] [Pn*ZrCl2]2LiCI THFx (0.114 mmol) and a metal salt of the desired ligand (M-L*, 0.229 mmol) were combined as solids in a Schlenk tube and toluene (3 ml_) was added at room temperature. When L = MeC(N'Pr)2 or PhC(N'Pr)2 solutions were stirred for 2 hours at room temperature and when L = HC(N-2,6-'Pr-C6H3)2 the solution was stirred at 60 °C for 15 h. In all cases all volatiles were removed in vacuo and the residues extracted into toluene and filtered through celite. Toluene was removed in vacuo and the products extracted into hexane and filtered to remove remaining LiCI. Crystals of each product were obtained by cooling concentrated hexane solutions to -30 °C. Crystals were isolated by filtration. [*Lithium salts were used for MeC(N'Pr)2 and PhC(N'Pr)2 whilst a potassium salt of HC(N-2,6-'Pr-C6H3)2 was used.]
[0085] Fig. 1 shows the 1H NMR spectrum of Pn*Zr(CI)(HC(N-2,6-'Pr-C6H3)2) recorded at 298 K in CD2CI2. The molecular structure is depicted in Fig. 2.
[0086] Fig. 3 shows the 1H NMR spectrum of Pn*Zr(CI)(MeC(N'Pr)2) recorded at 298 K in CeD6. The molecular dimeric structure is depicted in Fig. 4.
[0087] Fig. 5 shows the 1H NMR spectrum of Pn*Zr(CI)(PhC(N'Pr)2) recorded at 298 K in CeD6. The molecular structure is depicted in Fig. 6.
1.2. Procedure for the synthesis of Pn*Zr(CI)(HC(N-4-Me-C6H4)2)
[0088] [Pn*ZrCI2]2LiCI THFx (0.114 mmol) and K[HC(N-4-Me-C6H4)2] (0.229 mmol) were added to separate Schlenk tubes and each dissolved in toluene (2 ml_). The solution of the ligand was then added dropwise to that of [Pn*ZrCl2]2LiCI THFx at -20 °C to prevent double ligand substitution. The reaction was returned to room temperature and stirred for 1 h after which all volatiles volatiles were removed in vacuo. The residue was extracted into toluene and filtered (multiple times if required) to remove LiCI. Toluene was removed in vacuo and hexane added to precipitate the product.
[0089] Fig. 7 shows the 1H NMR spectrum of Pn*Zr(CI)(HC(N-4-Me-C6H4)2) recorded at 298 K in CD2CI2. The molecular dimeric structure is depicted in Fig. 8.
1.3. Procedure for the synthesis of Pn*Zr(Q-2,6-Me-C6H3)(PhC(NlPr)2)
[0090] [Pn*ZrCI2]2LiCI THFx (0.1 14 mmol) and K[PhC(N'Pr)2] (0.229 mmol) were combined in a schlenk tube and toluene (3 mL) was added and the solution stirred for 1 h. The reaction mixture was then transferred to a flask containing K[0-2,6-Me-C6H3] (0.229 mmol) and stirred for a further 1 hour. All volatiles were removed in vacuo and the residues extracted into toluene and filtered through celite. Toluene was removed in vacuo and the product was extracted into hexane and filtered to remove remaining LiCI. Crystals were obtained by cooling concentrated hexane solutions to -30 °C. Crystals were isolated by filtration.
[0091] Fig. 9 shows the 1 H NMR spectrum of Pn*Zr(0-2,6-Me-C6H3)(PhC(N'Pr)2) recorded at 298 K in C6D6. The molecular structure is depicted in Fig. 10.
Example 2 - Polymerisation studies
2.1. L-lactide polymerisation
[0092] The ability of the compounds of Example 1 to catalyse the polymerisation of L-lactide was assessed. Polymerisation experiments were conducted in a 0.5M L-lactide solution in Obϋd at 80 °C with 2 mol% [Zr]
[0093] Fig. 11 shows that all of the Example 1 compounds are potent catalysts for L-lactide polymerisation.
2.2. e-caprolactone polymerisation
[0094] The ability of Pn*Zr(0-2,6-Me-C6H3)(PhC(N'Pr)2) to catalyse the polymerisation of e- caprolactone was assessed. Polymerisation experiments were conducted in a 0.5M e- caprolactone solution in CeD6 at room temperature with 2 mol% Pn*Zr(0-2,6-Me- C6H3)(PhC(N'Pr)2).
[0095] Fig. 12 shows that Pn*Zr(0-2,6-Me-C6H3)(PhC(N'Pr)2) is a potent catalyst for e- caprolactone polymerisation.
Example 3 - Synthesis of further compounds
3.1. Procedure for the synthesis of Pn*Zr(('PrN)2C(4-R-C6H4))CI (R=OMe, CF3)
[0096] Pn*Zr{('PrN)2C(4-R-C6H4)}CI (R=OMe, CF3) was prepared by the reaction of 1 eq. [Pn*ZrCl2]2 LiCl thf2 with 2 eq. (l\rPr)2C(PhR) (R = OMe, CF3) in a NMR tube. The 1 H NMR spectra are shown in Figs. 13 and 14.
3.2. Procedure for the synthesis of Pn*Ti{(2,6-'PrC6H3N)2CH)CI
[0097] Rh*Tί{(2,6-'RGq6H3N)2qH}OI was synthesised by reaction of 1 eq. [Pn*TiCl2]2 with 2 eq. K{(2,6-'PrC6H3N)2CH}in a NMR tube. The 1 H NMR spectrum is shown in Fig. 15.
3.3. Procedure for the synthesis of )CI
[0098] Pn*Ti{('PrN)2C(C6H5)}CI was synthesised by reaction of 1 eq. [Pn*TiCl2]2 with 2 eq. Li{( 'PrN)2C(C6H5)}in a NMR tube. The 1 H NMR spectrum is shown in Fig. 16.
While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.
Claims
1. A compound having a structure according to formula I shown below:
X is selected from zirconium, hafnium and titanium;
Y is selected from:
i) halo, hydrogen, a phosphonate, sulfonate or borate anion,
ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, - NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NRaRb, aryl, (1- 6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or
iii) a ligand having a structure according to formula A below:
A wherein
each Rx is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-
6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy, and
Ry is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy;
each R1 is independently selected from (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1- 3C)fluoroalkyl, aryl and aryloxy; and
R2 is selected from hydrogen, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1- 3C)fluoroalkyl, aryl and aryloxy;
and wherein Ra and Rb are independently hydrogen or (1-4C)alkyl.
2. The compound of claim 1 , wherein X is zirconium.
3. The compound of claim 1 or 2, wherein each R1 group is independently selected from (1-6C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, - NRaRb, (1-6C)alkoxy, -C(0)NRaRb, (1-3C)fluoroalkyl, aryl and aryloxy.
4. The compound of any preceding claim, wherein each R1 group is independently
selected from (1-6C)alkyl and aryl, either of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (1-6C)alkoxy, aryl and aryloxy.
5. The compound of any preceding claim, wherein each R1 group is independently
selected from (1-4C)alkyl and phenyl, either of which is optionally substituted with 1-3 groups selected from halo, (1-4C)alkyl and (1-2C)alkoxy.
6. The compound of any preceding claim, wherein each R1 group is independently
selected from methyl, ethyl, isopropyl and tertbutyl, or each R1 group is independently a phenyl group that is optionally substituted with 1-3 groups selected from methyl, ethyl, isopropyl and tertbutyl.
7. The compound of any preceding claim, wherein both R1 groups are identical
8. The compound of any preceding claim, wherein R2 is selected from hydrogen, (1- 6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, -NRaRb and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-6C)alkyl, (2-6C)alkenyl, (2- 6C)alkynyl, (1-6C)alkoxy, (1-3C)fluoroalkyl, aryl and aryloxy.
9. The compound of any preceding claim, wherein R2 is selected from hydrogen, (1- 4C)alkyl and aryl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, aryl and aryloxy.
10. The compound of any preceding claim, wherein R2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, (1-2C)alkoxy, phenyl and phenoxy.
11. The compound of any preceding claim, wherein R2 is selected from hydrogen, (1- 4C)alkyl and phenyl, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
12. The compound of any preceding claim, wherein Y is
i) halo, hydrogen, a phosphonate, sulfonate or borate anion,
ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, -C(0)NRaRb, -NRaRb, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, nitro, -NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3, or iii) a ligand having a structure according to formula A, wherein each Rx has any of the definitions appearing in any preceding claim in relation to R1, and Ry has any of the definitions appearing in any preceding claim in relation to R2.
13. The compound of any preceding claim, wherein Y is
i) halo, or
ii) (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo, (1-4C)alkyl, - NRaRb, aryl, (1-6C)alkoxy, -C(0)NRaRb, and Si[(1-4C)alkyl]3.
14. The compound of any preceding claim, wherein Y is
i) halo, or
ii) (1-4C)alkyl, (1-4C)alkoxy, aryl and aryloxy, any of which is optionally substituted with one or more groups selected from halo and (1-4C)alkyl.
15. The compound of any preceding claim, wherein Y is
i) chloro, or
ii) (1-4C)alkoxy or a phenoxy group that is optionally substituted with 1 or 2 (1-4C)alkyl groups.
16. The compound of claim 1 , wherein the compound has any of the following structures:
17. The compound of claim 1 , wherein the compound has any of the following structures:
19. The compound of claim 1 , wherein the compound has any of the following structures:
20. The compound of any preceding claim, wherein the compound of formula (I) is immobilised on a solid support material.
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WO2015155214A2 (en) * | 2014-04-09 | 2015-10-15 | Scg Chemicals Co., Ltd. | Lactide polymerisation |
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WO2015155214A2 (en) * | 2014-04-09 | 2015-10-15 | Scg Chemicals Co., Ltd. | Lactide polymerisation |
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Title |
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DUNCAN A. X. FRASER ET AL: "Titanium and Zirconium Permethylpentalene Complexes, Pn*MCp R X, as Ethylene Polymerization Catalysts", ORGANOMETALLICS, vol. 35, no. 16, 22 August 2016 (2016-08-22), US, pages 2664 - 2674, XP055325330, ISSN: 0276-7333, DOI: 10.1021/acs.organomet.6b00417 * |
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