Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
  • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
  • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
  • C07D305/12—Beta-lactones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
  • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
  • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • 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
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • 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
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • 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
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
  • C08G63/56—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds other than from esters thereof
  • C08G63/58—Cyclic ethers; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters

Definitions

• the invention pertains to the field of chemical synthesis. More particularly, the invention pertains to novel molecules comprising lactones and anhydrides derived from glycidyl acrylates.
• US Patent No. 6,852,865 describes catalysts and methods for the carbonylation of epoxides, the methods therein can be used to make molecules of the present invention, however no examples of glycidyl acrylates as substrates are disclosed in the '865 patent.
• US 7,875,734 discloses the beta lactone derived from glycidyl methacrylate, but no uses for this compound are described.
• Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers.
• inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers.
• the compounds of the invention are enantiopure compounds. In certain other embodiments, mixtures of enantiomers or diastereomers are provided.
• certain compounds, as described herein may have one or more double bonds that can exist as either a Z or E isomer, unless otherwise indicated.
• the invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers.
• this invention also encompasses compositions comprising one or more compounds.
• isomers includes any and all geometric isomers and stereoisomers.
• “isomers” include cis- and iraws-isomers, E- and Z- isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention.
• a compound may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as
• a particular enantiomer may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched.”
• “Optically enriched,” as used herein, means that the compound is made up of a significantly greater proportion of one enantiomer. In certain embodiments the compound is made up of at least about 90% by weight of an enantiomer. In some embodiments the compound is made up of at least about 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9% by weight of an enantiomer.
• the enantiomeric excess of provided compounds is at least about 90%, 95%, 97%, 98%, 99%, 99.5%, 99.7%, 99.8%, or 99.9%.
• enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric syntheses. See, for example, Jacques, et al,
• halo and "halogen” as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -CI), bromine (bromo, -Br), and iodine (iodo, -I).
• aliphatic or "aliphatic group”, as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-30 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1-8 carbon atoms. In certain embodiments, aliphatic groups contain 1-6 carbon atoms.
• aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1 ⁇ 1 carbon atoms, in yet other embodiments aliphatic groups contain 1-3 carbon atoms, and in yet other embodiments aliphatic groups contain 1-2 carbon atoms.
• Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.
• heteroaliphatic refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, phosphorus, or boron.
• one or two carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus.
• Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include “heterocycle,” “hetercyclyl,” “heterocycloaliphatic,” or “heterocyclic” groups.
• epoxide refers to a substituted or unsubstituted oxirane.
• Substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further optionally substituted as defined herein.
• epoxides comprise a single oxirane moiety.
• epoxides comprise two or more oxirane moieties.
• glycol refers to an oxirane substituted with a hydroxyl methyl group or a derivative thereof.
• the term glycidyl as used herein is meant to include moieties having additional substitution on one or more of the carbon atoms of the oxirane ring or on the methylene group of the hydroxymethyl moiety, examples of such substitution may include, but are not limited to: alkyl groups, halogen atoms, aryl groups etc.
• the terms glycidyl ester, glycidyl acrylate, glydidyl ether etc. denote substitution at the oxygen atom of the above-mentioned hydroxymethyl group, i.e. that oxygen atom is bonded to an acyl group, an acrylate group, or an alkyl group respectively.
• acrylate or "acrylates” as used herein refer to any acyl group having a vinyl group adjacent to the acyl carbonyl.
• the terms encompass mono-, di- and trisubstituted vinyl groups.
• examples of acrylates include, but are not limited to: acrylate, methacrylate, ethacrylate, cinnamate (3-phenylacrylate), crotonate, tiglate, and senecioate. Because it is known that cylcopropane groups can in certain instances behave very much like double bonds, cyclopropane esters are specifically included within the definition of acrylate herein.
• polymer refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass.
• a polymer is comprised of only one monomer species (e.g., polyethylene oxide).
• a polymer of the present invention is a copolymer, terpolymer,
• heteropolymer block copolymer, or tapered heteropolymer of one or more epoxides.
• unsaturated as used herein, means that a moiety has one or more double or triple bonds.
• cycloaliphatic used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic, bicyclic, or polycyclic ring systems, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein.
• Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, and cyclooctadienyl.
• the cycloalkyl has 3-6 carbons.
• cycloaliphatic also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.
• a carbocyclic groups is bicyclic.
• a carbocyclic group is tricyclic.
• a carbocyclic group is polycyclic.
• alkyl refers to saturated, straight- or branched-chain hydrocarbon radicals derived from an aliphatic moiety containing between one and six carbon atoms by removal of a single hydrogen atom. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in yet other embodiments alkyl groups contain 1-3 carbon atoms, and in yet other embodiments alkyl groups contain 1-2 carbon atoms.
• alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec- hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.
• alkenyl denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2- ⁇ carbon atoms, in yet other embodiments alkenyl groups contain 2-3 carbon atoms, and in yet other embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, l-methyl-2- buten-l-yl, and the like.
• alkynyl refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms.
• alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2- ⁇ carbon atoms, in yet other embodiments alkynyl groups contain 2-3 carbon atoms, and in yet other embodiments alkynyl groups contain 2 carbon atoms.
• alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.
• Carbocycle and "carbocyclic ring” as used herein, refers to monocyclic and polycyclic moieties wherein the rings contain only carbon atoms. Unless otherwise specified, carbocycles may be saturated, partially unsaturated or aromatic, and contain 3 to 20 carbon atoms.
• Representative carbocyles include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bicyclo[2,2, l]heptane, norbornene, phenyl, cyclohexene, naphthalene, spiro[4.5]decane,
• aryl used alone or as part of a larger moiety as in “aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members.
• aryl may be used interchangeably with the term “aryl ring”.
• aryl refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents.
• aryl is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like.
• heteroaryl and “heteroar-”, used alone or as part of a larger moiety e.g., “heteroaralkyl”, or “heteroaralkoxy” refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 ⁇ electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms.
• heteroatom refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.
• Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl.
• heteroaryl and “heteroar-”, as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring.
• Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-l,4-oxazin-3(4H)-one.
• a heteroaryl group may be mono- or bicyclic.
• the term “heteroaryl” may be used interchangeably with the terms "heteroaryl ring"
• heteroaryl group or “heteroaromatic”, any of which terms include rings that are optionally substituted.
• heteroarylkyl refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted.
• heterocycle As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclic radical”, and
• heterocyclic ring are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered bicyclic heterocyclic moiety that is either saturated or partially unsaturated, and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above.
• nitrogen includes a substituted nitrogen.
• the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), ⁇ (as in pyrrolidinyl), or + NR (as in N-substituted pyrrolidinyl).
• a heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted.
• saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl.
• heterocycle refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions independently are optionally substituted.
• partially unsaturated refers to a ring moiety that includes at least one double or triple bond.
• partially unsaturated is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.
• compounds of the invention may contain "optionally substituted” moieties.
• substituted whether preceded by the term “optionally” or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent.
• an “optionally substituted” group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position.
• Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds.
• stable refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.
• substituents are shown attached to a bond which crosses a bond in a ring of the depicted molecule. This means that one or more of the substituents may be attached to the ring at any available position (usually in place of a hydrogen atom of the parent structure). In cases where an atom of a ring so substituted has two substitutable positions, two groups may be present on the same ring atom. When more than one substituent is present, each is defined independently of the others, and each may have a different structure. In cases where the substituent shown crossing a bond of the ring is -R, this has the same meaning as if the ring were said to be "optionally substituted" as described in the preceding paragraph.
• Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH 2 )o_4R°; -(CH 2 )o- 4 0R°;
• Suitable monovalent substituents on R° are independently halogen, -(CH 2 y 2 R e , -(haloR*), -(CH 2 y 2 OH, -(CH 2 y 2 OR e , -(CH 2 y 2 CH(OR') 2 ; -O(haloR'), -CN, -N 3 , -(CH 2 y 2 C(0)R e , -(CH 2 y 2 C(0)OH, -(CH 2 y 2 C(0)OR e , -(CH 2 )o- 4 C(0)N(R°) 2 ; -(CH 2 y 2 SR e , -(CH 2 y 2 SH, -(CH 2 y 2 NH 2 , -(CH 2 y 2 NHR e , -(CH 2 )o- 2 NR' 2 , -N0 2
• Suitable divalent substituents that are bound to vicinal substitutable carbons of an "optionally substituted” group include: -0(CR 2 ) 2 _ 3 0- wherein each independent occurrence of R is selected from hydrogen, Ci_6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• Suitable substituents on the aliphatic group of R * include halogen, -R", -(haloR"), -OH, -OR", -O(haloR'), -CN, -C(0)OH, -C(0)OR e , -NH 2 , -NHR", -NR' 2 , or -N0 2 , wherein each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently Ci_4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -iPh, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0 ⁇ 1 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -R ⁇ , -NR ⁇ 2 , -C(0)R ⁇ , -C(0)OR ⁇ , -C(0)C(0)R ⁇ , -C(0)CH 2 C(0)R ⁇ , - S(0) 2 R ⁇ , -S(0) 2 NR ⁇ 2 , -C(S)NR ⁇ 2 , -C( H)NR ⁇ 2 , or -N(R ⁇ )S(0) 2 R ⁇ ; wherein each R ⁇ is independently hydrogen, Ci_6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of R ⁇ , taken together with their intervening atom(s)
• Suitable substituents on the aliphatic group of R ⁇ are independently halogen, -R", -(haloR*), -OH, -OR", -O(haloR'), -CN, -C(0)OH, -C(0)OR e , -NH 2 , -NHR", -NR' 2 , or -N0 2 , wherein each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently Ci_4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0 -iPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0 ⁇ 1 heteroatoms independently selected from nitrogen, oxygen, or sulfur.
• catalyst refers to a substance the presence of which increases the rate of a chemical reaction, while not being consumed or undergoing a permanent chemical change itself.
• Tetradentate refers to ligands having four sites capable of coordinating to a single metal center.
• the present invention encompasses the recognition that bifunctional compounds having the combination of an acrylate moiety and a beta lactone or succinic anhydride functional group have utility as bifunctional reagents and as monomers for the production of new polymeric materials.
• the invention encompasses novel compounds having this combination of functional groups as well as methods to make and use them, and new polymers incorporating them. (I) Compounds of the invention.
• the present disclosure encompasses novel compounds conforming to formula I:
• R 1 , R 2 , and R 3 are each independently selected from the group consisting of: -H, optionally substituted Ci-12 aliphatic, optionally substituted Ci-12 heteroaliphatic, optionally substituted C6-14 aryl, and optionally substituted 5- to 14-membered heteroaryl; wherein, [R 1 and R 3 ] or [R 2 and R 3 ] can be taken together with intervening atoms to form an optionally substituted cylcoaliphatic or heterocyclic ring; and wherein R 1 and R 3 may be taken together to be a carbon-carbon bond (in which case R 2 is bonded to an alkyne); or wherein R , R , and R are R , R , and R , wherein: R 1 , R 2 , and R 3 are each independently selected from the group consisting of -H, Ci-6 aliphatic, and optionally substituted aryl;
• R 10 and R 11 are each independently selected from an optionally substituted group consisting of: -H, -F, optionally substituted Ci-12 aliphatic, optionally substituted Ci-12 heteroaliphatic, optionally substituted C6-14 aryl, and optionally substituted 5- to 14-membered heteroaryl; where R 10 and R 11 can can be taken together with the intervening carbon atom to form an optionally substituted spirocycle optionally containing one or more heteroatoms; or wherein R 10 and R 11 are R 12 and R 13 , wherein:
• R 12 and R 13 are each independently selected from the group consisting of -H, -F, optionally substituted Ci-6 aliphatic, and optionally substituted aryl; wherein R 12 and R 13 can be taken together with the intervening carbon atom to form an optionally substituted spirocycle;
• R 20 is optionally present, and if present is selected from the group consisting of -F, optionally substituted Ci-12 aliphatic, optionally substituted Ci-12 heteroaliphatic, optionally substituted C6-14 aryl, and optionally substituted 5- to 14-membered heteroaryl; when two or more R 20 groups are present, two or more of them can be taken together with intervening atoms to form one or more carbocycles or heterocycles.
• the present disclosure encompasses novel compounds conforming to formula I:
• R 1 , R 2 , and R 3 are each independently selected from the group consisting of: -H, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted C6-i 4 aryl, and optionally substituted 5- to 14-membered heteroaryl; wherein, [R 1 and R 3 ] or [R 2 and R 3 ] can be taken together with intervening atoms to form an optionally substituted cylcoaliphatic or heterocyclic ring; and wherein R 1 and R 3 may be taken together to be a carbon-carbon bond (in which case R 2 is bonded to an alkyne);
• R 10 and R 11 are each independently selected from an optionally substituted group consisting of: -H, -F, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted C6-i 4 aryl, and optionally substituted 5- to 14-membered heteroaryl; where R 10 and R 11 can can be taken together with the intervening carbon atom to form an optionally substituted spirocylcle optionally containing one or more heteroatoms; and
• R 20 is optionally present, and if present is selected from the group consisting of -F, optionally substituted C 1-12 aliphatic, optionally substituted C 1-12 heteroaliphatic, optionally substituted C6-i 4 aryl, and optionally substituted 5- to 14-membered heteroaryl; when two or more R 20 groups are present, two or more of them can be taken together with intervening atoms to form one or more carbocycles or heterocycles.
• R , R R ⁇ R , R , and R ⁇ is as defined above and in the classes and subclasses herein.
• a compound is of formula I or II, wherein R 10 and R 11 are each independently selected from an optionally substituted group consisting of: -H, -F, optionally substituted Ci-12 aliphatic, optionally substituted Ci-12 heteroaliphatic, optionally substituted C6-14 aryl, and optionally substituted 5- to 14-membered heteroaryl; where R 10 and R 11 can can be taken together with the intervening carbon atom to form an optionally substituted spirocycle optionally containing one or more heteroatoms.
• a compound is of formula I or II, wherein R 10 and R 11 are R 12 and R 13 .
• R 20 is absent and the present disclosure encompasses compounds of formula la or Ila:
• R ⁇ R , R R , and R is as defined above and in the classes and subclasses herein.
• the present disclosure encompasses compounds of formula lb:
• R ⁇ ir, R R , and R 1J are as defined above and in the classes and subclasses herein.
• the present disclosure encompasses compounds of formula lb:
• R 12 and R 13 are each independently selected from the group consisting of -H, -F, optionally substituted Ci-6 aliphatic, and optionally substituted C6-10 aryl, wherein R 12 and R 13 can be taken together with the intervening carbon atom to form an optionally substituted spirocycle.
• the present disclosure encompasses compounds of formula lib:
• R 1 ' , R 2' , and R 3' are each independently selected from the group consisting of -H, Ci-6 aliphatic, and optionally substituted Ce-w aryl.
• R 1 , R 2 , R 3 and R 12 are as defined above.
• the present disclosure encompasses a composition comprising any one or more of the compounds from Tables la and lb. In certain embodiments, the present disclosure encompasses a composition comprising any single compound from Table la or lb. embodiment, the present disclosure encompasses a composition comprising
• the present disclosure encompasses a composition
• the present disclosure encompasses a composition
• the present disclosure encompasses a composition
• the present disclosure encompasses a composition
• the present disclosure encompasses a composition comprising any one or more of the compounds from Tables Ila or lib. In certain embodiments, the present disclosure encompasses a composition comprising any single compound from Table Ila or lib.
• the present disclosure encompasses a composition comprising
• the present disclosure encompasses a composition
• the present disclosure encompasses a composition
• the present disclosure encompasses a composition
• the present disclosure encompasses a composition
• compositions comprising the compound in another embodiment, the present disclosure encompasses a composition
• the present disclosure encompasses a composition
• the compounds have not been drawn with stereochemistry indicated. It is to be understood that the racemic compounds as well as their enantioenriched counterparts are encompassed by the present disclosure.
• the glycidyl moiety in molecules of the invention may be racemic, enantioenriched, or enantiopure.
• the present disclosure therefore encompasses compounds (R)-I, and (S)-l and mixtures thereof as well as compounds (R)-II, and (S)-1I and mixtures thereof:
• R , R , R R , R , and R u are as defined above and in the classes and subclasses herein.
• compounds of the invention are provided as racemic mixtures. In other embodiments, compounds of the invention are provided as enantiomerically- or diastereotopically-enriched form. In certain embodiments, the compounds are provided in greater than 70% enantiopurity. In other embodiments, the compounds are provided in greater than 80% enantiopurity. In other embodiments, the compounds are provided in greater than 90% enantiopurity. In other embodiments, the compounds are provided in greater than 95% enantiopurity. In other embodiments, the compounds are provided in greater than 99% enantiopurity.
• the compounds are provided in essentially enantiopure form.
• the compounds of the present invention also contain minor amounts regioisomeric compounds.
• compounds of the present invention comprise a compound of formula I in combination with a compound of formula I-r:
• R , R , R J , R , R , and R u is as defined above and in the classes and subclasses herein.
• the present invention encompasses compounds of formula la, lb, Ic, or any compound of Tables la or lb, characterized in that they contain the corresponding regioisomer conforming to formula I-r.
• the regioisomer conforming to formula I-r is present in an amount from about 0.001% to about 10% based on the major isomer corresponding to formula I. In certain embodiments, the regioisomer I-r is present in an amount between 0.001% and 0.5%, or between about 0.1% and 1%, or between about 0.2% and 2%, or between about 0.5% and 5%, or between about 5% and 10%. In certain embodiments the present invention encompasses compounds of any of formulae I, la, lb, Ic, or a compound of Tables la or lb with the proviso that the compound not have the structure .
• the present invention encompasses compounds of formula I, or a compound of Tables la or lb with the proviso that the compound not have the structure . In certain embodiments the present invention encompasses compounds of formula I, with the proviso that the compound not have the structure . in certain embodiments the present invention encompasses a compounds from Table la, with the proviso that the compound not have the structure or .
• the present invention encompasses compounds of any of formulae II, Ila, or lib, with the proviso that the compound not have the structure . In certain embodiments the present invention encompasses compounds compounds of any Ila, or lib, with the proviso that the compound not
• the present invention encompasses compounds compounds of any of formulae II, Ila, or lib, with the proviso
• methods of the present invention include the step of carbonylating a glycidyl acrylate of formula III to yield a ring-expanded product comprising a ⁇ -lactone of structure I as shown in Scheme 1 :
• the method of Scheme 1 includes the step of contacting a compound of formula III with a catalyst comprising a transition metal carbonyl complex under an atmosphere comprising carbon monoxide gas.
• Catalyst compositions and reaction conditions suitable for performing the carbonylation step of Scheme 1 are disclosed in US Patent Nos. 5,310,948; 5,359,081; 6,852,865; 7, 145,022; 7,420,064, and US 7,569,709 and in pending application PCT/US12/52857. The entirety of each of the above-referenced documents is hereby incorporated herein by reference.
• the method of the Scheme 1 comprises the step contacting a compound III with an atmosphere containing a partial pressure of CO between about 1 atm and about 130 atm.
• the carbon monoxide pressure is in the range of from about 50 psi to about 2000 psi. In certain embodiments, the carbon monoxide pressure is in the range of from about 300 psi to about 1000 psi. In certain embodiments, the carbon monoxide pressure is in the range of from about 400 psi to about 700 psi.
• the method of Scheme 1 includes the step of contacting compound III with a catalyst containing a metal carbonyl complex having the formula (M) y L Scheme(CO) x where M is a transition metal, L is a coordinating ligand and need not be present, y denotes the number of metal atoms in the complex and is an integer from 1 to 6, n denotes the number of coordinating ligands present in the complex and is an integer from 0 to 6, and x represents the number of carbon monoxide ligands in the complex is an integer from 1 to 16.
• the metal carbonyl complex is neutral. In other cases the metal carbonyl complex is charged.
• the metal carbonyl complex is anionic.
• the metal carbonyl complex comprises a transition metal from Groups 8, 9, or 10. In some embodiments, the metal carbonyl complex comprises a cobalt carbonyl complex. In certain embodiments, the metal carbonyl complex comprises a carbonyl cobaltate anion.
• the method of Scheme 1 includes the step of contacting compound III with a catalyst comprising a metal carbonyl complex in combination with a Lewis acidic co-catalyst.
• the Lewis acidic co-catalyst comprises a neutral Lewis acid while in other embodiments, the Lewis acidic co-catalyst is cationic.
• the Lewis acid co-catalyst comprises a metal-ligand complex.
• the Lewis acid co-catalyst comprises a cationic metal-ligand complex comprising a metal atom coordinated with a multidentate ligand.
• the Lewis acidic co-catalyst comprises a chromium or aluminum atom coordinated with a tetradentate ligand comprising a porphyrin or salen moiety.
• these aluminum or chromium complexes are cationic.
• the method of Scheme 1 comprises contacting compound III with a catalyst comprising a cationic aluminum or chromium complex in combination with an anionic metal carbonyl complex.
• the catalyst comprises a cationic aluminum-centered Lewis acid in combination with a carbonyl cobaltate anion.
• the catalyst comprises a cationic chromium-centered Lewis acid in combination with a carbonyl cobaltate anion.
• the catalyst is chosen from among those disclosed in US Patent No. 6,852,865 and in US Patent Application Serial No. 12/204,411.
• the method of Scheme 1 includes the step of dissolving or suspending compound III and the carbonylation catalyst in a solvent and contacting the resulting solution or suspension with the carbon monoxide atmosphere.
• the solvent of this step should be able to dissolve the starting glycidyl acrylate to some extent and should also dissolve and be unreactive toward the catalyst(s) employed.
• the optimal choice of solvent may vary depending on the substrate to be carbonylated and the catalyst system employed, but in general aprotic solvents of medium to high polarity are suitable as a reaction medium.
• the solvent comprises an ether such as DME, THF, TBME, diethyl ether, or dioxane.
• the solvent comprises a non-protic polar solvent such as ethyl acetate, propyl acetate, acetonitrile, acetone, nitromethane, or DMF.
• the solvent comprises a halogenated solvent such as dichloromethane, chloroform, or trichloroethane.
• the solvent may comprise an aromatic compound such as benzene, toluene, or xylene.
• the solvent is chosen from the group consisting of toluene, xylene, mesitylene, and 1,4-dioxane.
• the step of carbonylating compound III is conducted at a temperature of from about -20 to about 100 °C. In certain embodiments, the reaction is conducted at a temperature in the range of about 30 to about 90 °C. In certain
• the reaction is conducted at a temperature in the range of about 60 to about 80 °C.
• the method of Scheme 1 includes the steps of initiating the reaction at a temperature below ambient, then allowing the reaction to warm.
• the method includes the steps of initiating the reaction at a low temperature and then heating the mixture to a temperature in the range of about 30 to about 90 °C.
• methods of Scheme 1 include one or more steps to monitor the progress of the reaction. This can be done by well known means such as in situ measurement of the IR absorbance spectrum of the reaction mixture or by analyzing aliquots of the reaction mixture for the disappearance of starting the materials III and/or the accumulation of products I. Suitable methods for the latter include, but are not limited to chromatographic methods such as GC, HPLC, TLC, and spectroscopic methods such as NMR, IR, UV-vis and mass spectroscopy.
• the methods of Scheme 1 may optionally include the further step of stopping the reaction when the conversion has proceeded to a desired degree. Stopping the reaction may comprise one or more steps including cooling the reaction mixture, venting the reaction mixture, adding one or more quenching reagents, diluting the reaction mixture, and stripping solvents or volatiles from the reaction mixture. A further step of purifying the products of the reaction may also be included.
• the method of Scheme 1 includes the step of contacting compound III with carbon monoxide in a continuous flow process. In certain embodiments, the method of Scheme 1 includes the step of contacting compound III with carbon monoxide in a batch process.
• methods of the present invention include the step of carbonylating a substituted ⁇ -lactone of formula I to provide a ring expanded product comprising a substituted succinic anhydride derivative of formula II as shown in Scheme 2:
• the method of Scheme 2 comprises the step of contacting a compound of formula I with a catalyst comprising a transition metal carbonyl complex under an atmosphere comprising carbon monoxide gas.
• Catalyst compositions and reaction conditions suitable for performing the carbonylation step of Scheme 2 are disclosed in US Patent Nos. 6,852,865; 7,145,022; and 7,420,064, in US Patent
• the method of the Scheme 2 comprises the step of contacting a compound I with an atmosphere containing a partial pressure of CO between about 1 atm and about 130 atm.
• the carbon monoxide pressure is in the range of from about 50 psi to about 2000 psi. In certain embodiments, the carbon monoxide pressure is in the range of from about 300 psi to about 1000 psi. In certain embodiments, the carbon monoxide pressure is in the range of from about 400 psi to about 700 psi.
• the method of Scheme 2 includes the step of contacting compound I with a catalyst comprising a metal carbonyl complex having the formula (M)yL Scheme(CO) x where M is a transition metal, L is a coordinating ligand and need not be present, y denotes the number of metal atoms in the complex and is an integer from 1 to 6, n denotes the number of coordinating ligands present in the complex and is an integer from 0 to 6, and x represents the number of carbon monoxide ligands in the complex is an integer from 1 to 16.
• the metal carbonyl complex is neutral. In other cases the metal carbonyl complex is charged.
• the metal carbonyl complex is anionic.
• the metal carbonyl complex comprises a transition metal from Groups 8, 9, or 10. In some embodiments, the metal carbonyl complex comprises a cobalt carbonyl complex. In certain embodiments, the metal carbonyl complex comprises a carbonyl cobaltate anion. In certain embodiments, the method of Scheme 2 includes the step of contacting compound I with a catalyst comprising a metal carbonyl complex in combination with a Lewis acidic co-catalyst. In some embodiments, the Lewis acidic co-catalyst comprises a neutral Lewis acid, while in other embodiments, the Lewis acidic co-catalyst is cationic. In certain embodiments, the Lewis acid co-catalyst comprises a metal-ligand complex.
• the Lewis acid co-catalyst comprises a cationic metal-ligand complex comprising a metal atom coordinated with a multidentate ligand.
• the Lewis acidic co-catalyst comprises a chromium or aluminum atom coordinated with a tetradentate ligand comprising a porphyrin or salen moiety.
• these aluminum or chromium complexes are cationic.
• the method of Scheme 2 includes the step of contacting compound I with a catalyst system comprising a cationic aluminum or chromium complex in combination with an anionic metal carbonyl complex.
• the catalyst system comprises a cationic aluminum-centered Lewis acid in combination with a carbonyl cobaltate anion. In other embodiments, the catalyst system comprises a cationic chromium-centered Lewis acid in combination with a carbonyl cobaltate anion. In certain embodiments, the catalyst is chosen from among those disclosed in US Patent No.
• the method of Scheme 2 is comprises dissolving compound I and the carbonylation catalyst in a solvent that is in contact with the carbon monoxide atmosphere.
• the solvent of this step should be able to dissolve the starting glycidylacrylate to an appreciable extent, and should also dissolve and be unreactive toward the catalyst(s) employed.
• the optimal choice of solvent may vary depending on the substrate to be carbonylated and the catalyst system employed, but in general aprotic solvents of medium to high polarity are suitable as a reaction medium.
• the solvent comprises an ether such as DME, THF, TBME, diethyl ether, or dioxane.
• the solvent comprises a non-protic polar solvent such as ethyl acetate, propyl acetate, acetonitrile, acetone, nitromethane, or DMF.
• the solvent comprises a halogenated solvent such as dichloromethane, chloroform, or trichloroethane.
• the solvent may comprise an aromatic compound such as benzene, toluene, or xylene.
• the step of carbonylating compound I is conducted at a temperature of from about -20 to about 100 °C. In certain embodiments, the reaction is conducted at a temperature in the range of about 30 to about 90 °C. In certain
• the reaction is conducted at a temperature in the range of about 60 to about 80 °C.
• the method of Scheme 2 includes the steps of initiating the reaction at a temperature below ambient, then allowing the reaction to warm.
• the method includes the steps of initiating the reaction at a low temperature and then heating the mixture to a temperature in the range of about 30 to about 90 °C.
• methods of Scheme 1 include one or more steps to monitor the progress of the reaction. This can be done by well known means such as in situ monitoring the IR absorbance spectrum of the reaction mixture, or by analyzing aliquots of the reaction for the disappearance of starting materials I and/or the
• the method of Scheme 2 may optionally comprise the further step of stopping the reaction when the conversion has proceeded to a desired degree. Stopping the reaction may comprise one or more steps including but not limited to: cooling the reaction mixture, venting the reaction mixture, adding one or more quenching reagents, diluting the reaction mixture, and stripping solvents or volatiles from the reaction mixture. A further step of isolating the products of formula II from the reaction may also be included.
• the method of Scheme 2 includes the step of contacting compound I with carbon monoxide in a continuous flow process. In certain embodiments, the method of Scheme 2 includes the step of contacting compound I with carbon monoxide in a batch process.
• methods of the present invention include the step of doubly carbonylating a glycidyl acrylate of formula III to provide a ring expanded product comprising a substituted succinic anhydride derivative of formula II as shown in Scheme 3:
• the method of Scheme 3 comprises the step of contacting a compound of formula III with a catalyst comprising a transition metal carbonyl complex under an atmosphere comprising carbon monoxide gas.
• Catalyst compositions and reaction conditions suitable for performing the carbonylation step of Scheme 3 are disclosed in US Patent Application Serial Nos. 12/204,41 1 and 61/040,944 the entirety of each of which is hereby incorporated herein by reference.
• the method of the Scheme 3 comprises the step of contacting a compound III with an atmosphere containing a partial pressure of CO between about 1 atm and about 130 atm.
• the carbon monoxide pressure is in the range of from about 50 psi to about 2000 psi. In certain embodiments, the carbon monoxide pressure is in the range of from about 300 psi to about 1000 psi. In certain embodiments, the carbon monoxide pressure is in the range of from about 400 psi to about 700 psi.
• the method of Scheme 3 includes the step of contacting compound III with a catalyst comprising a metal carbonyl complex having the formula (M)yL Scheme(CO) x where M is a transition metal, L is a coordinating ligand and need not be present, y denotes the number of metal atoms in the complex and is an integer from 1 to 6, n denotes the number of coordinating ligands present in the complex and is an integer from 0 to 6, and x represents the number of carbon monoxide ligands in the complex is an integer from 1 to 16.
• the metal carbonyl complex is neutral. In other cases the metal carbonyl complex is charged.
• the metal carbonyl complex is anionic.
• the metal carbonyl complex comprises a transition metal from Groups 8, 9, or 10. In some embodiments, the metal carbonyl complex comprises a cobalt carbonyl complex. In certain embodiments, the metal carbonyl complex comprises a carbonyl cobaltate anion.
• the method of Scheme 3 includes the step of contacting compound III with a catalyst comprising a metal carbonyl complex in combination with a Lewis acidic co-catalyst.
• the Lewis acidic co-catalyst comprises a neutral Lewis acid, while in other embodiments, the Lewis acidic co-catalyst is cationic.
• the Lewis acid co-catalyst comprises a metal-ligand complex.
• the Lewis acid co-catalyst comprises a cationic metal-ligand complex comprising a metal atom coordinated with a multidentate ligand.
• the Lewis acidic co-catalyst comprises a chromium or aluminum atom coordinated with a tetradentate ligand comprising a porphyrin or salen moiety.
• these aluminum or chromium complexes are cationic.
• the method of Scheme 3 includes the step of contacting compound III with a catalyst system comprising a cationic aluminum or chromium complex in combination with an anionic metal carbonyl complex.
• the catalyst system comprises a cationic aluminum-centered Lewis acid in combination with a carbonyl cobaltate anion. In other embodiments, the catalyst system comprises a cationic chromium-centered Lewis acid in combination with a carbonyl cobaltate anion. In certain embodiments, the catalyst is chosen from among those disclosed in US Patent No. 6,852,865 and in pending US Patent Application Serial No. 12/204,41 1.
• the method of Scheme 3 includes the step of dissolving compound III and the carbonylation catalyst in a solvent that is in contact with the carbon monoxide atmosphere.
• the solvent of this step should be able to dissolve the starting glycidylacrylate to an appreciable extent, and should also dissolve and be unreactive toward the catalyst(s) employed.
• methods of the invention are improved by the presence of a solvent that includes a Lewis base.
• Lewis base refers to any nucleophilic species that is capable of donating an electron pair.
• the Lewis base is distinct from the epoxide. In other embodiments, the Lewis base is the epoxide (i.e., the reaction is performed in neat epoxide).
• the solvent used will fully dissolve the substrate III and provide a reaction mixture in which the catalyst employed is at least partially soluble.
• Suitable solvents may include ethers, ketones, aromatic hydrocarbons, halocarbons, esters, nitriles, and some alcohols.
• a suitable solvent may include: 1,4-dioxane; tetrahydrofuran; tetrahydropyran; dimethoxyethane; glyme; diethyl ether; t-butyl methyl ether; 2,5-dimethyl tetrahydrofuran; ethyl acetate; propyl acetate; butyl acetate; acetone; 2-butanone; cyclohexanone; toluene; acetonitrile; and difluorobenzene.
• the solvent includes 1,4- dioxane, toluene, and/or dimethoxyethane.
• solvent includes 1,4- dioxane.
• Mixtures of two or more of the above solvents are also useful, and in some cases may be preferred to a single solvent.
• mixtures of toluene and 1,4-dioxane are useful.
• the solvent may include a Lewis base with lower electron donicity than tetrahydrofuran.
• the solvent may include a Lewis base with lower electron donicity than 2-methyltetrahydrofuran.
• the solvent may include a Lewis base with lower electron donicity than 2,5-dimethyltetrahydrofuran.
• the solvent may include a Lewis base with higher electron donicity than difluorobenzene.
• the solvent may include a Lewis base with higher electron donicity than toluene.
• the solvent may include a Lewis base with substantially the same electron donicity as 1,4-dioxane.
• the step of doubly carbonylating compound III is conducted at a temperature of from about -20 to about 100 °C.
• the reaction is conducted at a temperature in the range of about 30 to about 90 °C.
• the reaction is conducted at a temperature in the range of about 60 to about 80 °C.
• the method of Scheme 3 includes the steps of initiating the reaction at a temperature below ambient, then allowing the reaction to warm.
• the method includes the steps of initiating the reaction at a low temperature and then heating the mixture to a temperature in the range of about 30 to about 90 °C.
• methods of Scheme 3 include one or more steps to monitor the progress of the reaction. This can be done by well known means such as in situ monitoring the IR absorbance spectrum of the reaction mixture, or by analyzing aliquots of the reaction for the disappearance of starting materials III and/or the accumulation of products II. Suitable methods for the latter include, but are not limited to GC, HPLC, TLC, NMR, and mass spectroscopy.
• the method of Scheme 3 may optionally comprise the further step of stopping the reaction when the conversion has proceeded to a desired degree. Stopping the reaction may comprise one or more steps including but not limited to: cooling the reaction mixture, venting the reaction mixture, adding one or more quenching reagents, diluting the reaction mixture, and stripping solvents or volatiles from the reaction mixture. A further step of isolating the products of formula II from the reaction may also be included.
• the method of Scheme 3 includes the step of contacting compound III with carbon monoxide in a continuous flow process.
• the method of Scheme 3 includes the step of contacting compound III with carbon monoxide in a batch process.
• methods of the present invention encompasses
• methods of the present invention encompasses
• the present invention encompasses the use of lactones of formulae I or II as bifunctional monomers.
• the acrylate functional group of I or II is polymerized using methods well known in the art to provide an acrylate polymer with lactone or anhydride side-chains—the latter are denoted by Z in Scheme 4 as shown below:
• R , R R R , R , and are as defined above and described in the classes and subclasses herein and n is an integer from 1 to about 100,000.
• the reactive Z groups in polymers PI in Scheme 4 can be further manipulated to introduce other functionality via ring-opening reactions with nucleophilic groups such as alcohols, water, amines, and thiols.
• nucleophilic groups such as alcohols, water, amines, and thiols.
• the Z groups can be used to cross-link the polymers by addition of polyols, polyamines, amino alcohols and the like.
• the lactone when the Z group is a beta lactone, the lactone can be pyrolized to form an alkene:
• the compounds I and II can be used alone as monomers to afford heavily functionalized polymers.
• monomers I and II can be co-polymerized with one or more additional alkenes such as ethylene, propylene, higher alpha olefins, styrene, divinyl benzene, vinyl toluene, acrylonitrile, butadiene, isobutylene and the like to provide functionalized polyolefins.
• they can be co- polymerized with one or more additional acrylates such as acrylic acid, methacrylic acid, crotonic acid, or their esters or amides to provide functionalized co-polymers.
• the lactone functional group of compounds of formula I can be polymerized using methods well known in the art to provide polyhydroxypropionate polymers with acrylate side-chains (denoted P2 in Scheme
• R , R R R , R , and are as defined above and described in the classes and subclasses herein and n is an integer from 1 to about 100,000.
• the acrylate side-chains can now serve as reactive groups for further reaction by radical chemistry, Michael addition, etc., to further functionalize or to cross-link the polymer.
• the present invention provides copolymers arising from the copolymerization of monomer I with other monomers.
• Suitable other monomers include but are not limited to lactide, beta propiolactone, beta butyrolactone, gamma caprolactone, glycolide and the like.
• Additional monomer units in the polymer chain P2 can be derived from compounds such as diols, diacids, hydroxy acids, carbon dioxide, epoxides, phosgene, dialkyl carbonates, isocyanates, and combinations of any two or more of these.
• the present invention encompasses random-, block-, or tapered-copolymers of I with any one or more of these comonomers. It will be recognized that many variations of the inventive copolymers can be formed by manipulation of the polymerization conditions including but not limited to the ratio of monomers provided, the catalyst(s) employed, and the timing of addition of the monomers and/or catalysts. Similarly, compounds of formula II, can be polymerized via their anhydride functionality.
• R , R , R R , R , and R u are as defined above and described in the classes and subclasses herein; R 30 is optionally present, and if present is defined as R 20 described hereinabove; and n is an integer from 1 to about 100,000.
• the bifunctional molecules I and II are useful as reagents for surface modifications of items such as wood, textiles, papers, and polymers.
• the free hydroxyl groups of the cellulose in wood or paper can be made to react with the anhydride moiety of II or the beta lactone of I to covalently link the compound to the cellulosic material.
• the acrylate sidechain can then act as a site for further chemical modification using other chemistries such as radical, cationic,or anionic polymerization, Michael additions etc. to modify the properties of the surface.

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