EP4554922A2 - Verfahren zur herstellung eines alkens aus einem polymer - Google Patents

Verfahren zur herstellung eines alkens aus einem polymer

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Publication number
EP4554922A2
EP4554922A2 EP23840363.8A EP23840363A EP4554922A2 EP 4554922 A2 EP4554922 A2 EP 4554922A2 EP 23840363 A EP23840363 A EP 23840363A EP 4554922 A2 EP4554922 A2 EP 4554922A2
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EP
European Patent Office
Prior art keywords
substituted
unsubstituted
membered
dehydrogenated
substituent group
Prior art date
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Pending
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EP23840363.8A
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English (en)
French (fr)
Inventor
John F. Hartwig
Steven Hanna
Richard J. CONK
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University of California
University of California Berkeley
University of California San Diego UCSD
Original Assignee
University of California
University of California Berkeley
University of California San Diego UCSD
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Application filed by University of California, University of California Berkeley, University of California San Diego UCSD filed Critical University of California
Publication of EP4554922A2 publication Critical patent/EP4554922A2/de
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25—Migration of carbon-to-carbon double bonds
    • C07C5/2506—Catalytic processes
    • C07C5/2562—Catalytic processes with hydrides or organic compounds
    • C07C5/2593—Catalytic processes with hydrides or organic compounds containing phosphines, arsines, stibines or bismuthines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/26—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • BACKGROUND [0003] The conversion of polyolefins to small molecules (e.g., monomers) would enable the largest fraction of waste plastic to be a carbon feedstock, but such a task requires cleavage of carbon-carbon bonds that often resist selective chemical transformations. Disclosed herein, inter alia, are solutions to these and other problems in the art.
  • BRIEF SUMMARY [0004] In an aspect is provided a method of making an alkene, the method including mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s). In embodiments, the method includes mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s).
  • the dehydrogenated polymer includes at most 10% unsaturated alkene monomer units. In embodiments, the dehydrogenated polymer includes at least 20 carbon atoms. In embodiments, prior to the mixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer.
  • the method includes mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (i) the dehydrogenated polymer includes at most 10% unsaturated alkene monomer units; (ii) the dehydrogenated polymer includes at least 20 carbon atoms; or (iii) prior to the mixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer.
  • a method of making a dehydrogenated polymer including mixing a polymer with one or more dehydrogenating reagent(s), wherein: (i) a percentage of from 0.01% to 1.5% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.7% to 2.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 2.4% to 4.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated.
  • the method includes mixing a polymer with one or more dehydrogenating reagent(s), wherein: (i) a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated; (ii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (iii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of 0.01% to 10% of monomer units are unsaturated; or (iv) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.
  • the dehydrogenated polymer has a number average molecular weight of about 100 Da to about 2,200 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da.
  • a method of degrading a substance including: (i) conducting one or more reaction(s) to form one or more olefin units in the substance; (ii) subjecting, after step (i), to conditions for olefin metathesis; and (iii) subjecting, after step (i), to conditions for olefin isomerization.
  • a method of making a substituted or unsubstituted alkene including subjecting a dehydrogenated polymer to conditions for metathesis and to conditions for olefin isomerization.
  • a method of making a substituted or unsubstituted alkene comprising subjecting a first substance to conditions for metathesis and to conditions for olefin isomerization; wherein: (i) the first substance includes at least 20 carbon atoms per molecule; or (ii) prior to subjecting the first substance to conditions for metathesis and to conditions for olefin isomerization, the method includes subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.
  • a substituted or unsubstituted dehydrogenated polyethylene wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are unsaturated (e.g., olefinic, e.g., monoenes). In embodiments, a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are olefinic. In embodiments, a percentage of from 0.01% to 1.5% of monomer units are olefinic. In embodiments, a percentage of from 1.7% to 2.3% of monomer units are olefinic.
  • FIGS.1A-1D Strategies for the valorization of PE waste.
  • FIG.1A Degradation of PE by alkane metathesis with n-hexane (Huang 2016, Román-Leshkov 2021).
  • FIG.1B Conversion of PE to alkyl aromatics by tandem hydrogenolysis/aromatization (Scott 2020).
  • FIG.1C Degradation of PE by hydrogenolysis.
  • FIGS.2A-2D Conditions tested for DIE.
  • FIG.2A Homogeneous dehydrogenation of PE. Conditions for dehydrogenation: 0.42 mol % Ir- tBu POCOP, 0.46 mol % NaOtBu, 0.6M in PE, reactions run for 12 h with 0.4 equiv TBE (mol %, equiv TBE, and M of PE calculated relative to PE monomer units).
  • FIG.2C GPC Chromatogram of HDPE prior to and after ethenolysis with M-1. Conditions for ethenolysis were: 0.36 M in unsaturated PE 3.6 mol% M-1 in p-xylene, heated to 130 °C for 16 h under 25 bar ethylene.
  • FIG.2D Sequential dehydrogenation and ethenolysis of a long chain paraffin (C24H50). Initial dehydrogenation yields olefins in 10% yield, and subsequent ethenolysis with M-1 yields a statistical distribution of shorter-chain olefins.
  • FIGS.3A-3C Development of conditions for DIE of PE.
  • FIG.3A Optimization of catalyst combinations for IE of 1-octadecene. Conditions: 1-octadecene (0.5 M) was combined with isomerization (3.0 mol%) and metathesis (6.0 mol%) catalysts in p-xylene and heated to 60 °C under 25 bar of ethylene for 16 h.
  • FIG. 3B Application of IE to dehydro-polyethylene, with dehydro-HDPE yielding a maximum of 80% propene with 1.96% dehydrogenation.
  • FIG. 3C DIE of 13 C-labeled HDPE to check for background reactivity (conditions identical to those in FIG.3B).
  • FIG.4. DIE of post-consumer PE (conditions identical to those in FIG.3B).
  • Propene yields are reported as XX%(YY) where X is the yield obtained from polymer purified by precipitation from acetone, and Y is the yield obtained from unmodified polymer. Where a single yield is reported, dehydrogenation on unpurified samples failed.
  • FIGS.5A-5E Investigation of reaction scope and kinetics.
  • FIG.5C Yields of IE on small molecules 1a-1d designed to assess the effect of branching on IE.
  • FIG.5D Yields of IE on small molecules 1e-1f designed to test the effect of dienes on IE.
  • alkyl by itself or as part of another substituent, means, unless otherwise stated, a straight (i.e., unbranched) or branched carbon chain (or carbon), or combination thereof, which may be fully saturated, mono- or polyunsaturated and can include mono-, di-, and multivalent radicals.
  • the alkyl may include a designated number of carbons (e.g., C 1 -C 10 means one to ten carbons).
  • Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2- propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and the higher homologs and isomers.
  • An alkoxy is an alkyl attached to the remainder of the molecule via an oxygen linker (-O-).
  • An alkyl moiety may be an alkenyl moiety.
  • An alkyl moiety may be an alkynyl moiety.
  • An alkyl moiety may be fully saturated.
  • a heteroalkyl moiety may include one heteroatom (e.g., O, N, S, Si, or P).
  • a heteroalkyl moiety may include two optionally different heteroatoms (e.g., O, N, S, Si, or P).
  • a heteroalkyl moiety may include three optionally different heteroatoms (e.g., O, N, S, Si, or P).
  • a heteroalkyl moiety may include four optionally different heteroatoms (e.g., O, N, S, Si, or P).
  • heteroalkynyl may optionally include more than one triple bond and/or one or more double bonds in additional to the one or more triple bonds.
  • heteroalkylene by itself or as part of another substituent, means, unless otherwise stated, a divalent radical derived from heteroalkyl, as exemplified, but not limited by, -CH2-CH2-S-CH2-CH2- and -CH2-S-CH2-CH2-NH-CH2-.
  • heteroatoms can also occupy either or both of the chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like).
  • heteroalkyl is recited, followed by recitations of specific heteroalkyl groups, such as -NR'R'' or the like, it will be understood that the terms heteroalkyl and -NR'R'' are not redundant or mutually exclusive. Rather, the specific heteroalkyl groups are recited to add clarity. Thus, the term “heteroalkyl” should not be interpreted herein as excluding specific heteroalkyl groups, such as -NR'R'' or the like. [0022]
  • Cycloalkyl and heterocycloalkyl are not aromatic. Additionally, for heterocycloalkyl, a heteroatom can occupy the position at which the heterocycle is attached to the remainder of the molecule.
  • Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like.
  • the term “cycloalkyl” means a monocyclic, bicyclic, or a multicyclic cycloalkyl ring system.
  • monocyclic ring systems are cyclic hydrocarbon groups containing from 3 to 8 carbon atoms, where such groups can be saturated or unsaturated, but not aromatic.
  • cycloalkyl groups are fully saturated.
  • monocyclic cycloalkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, and cyclooctyl.
  • Bicyclic cycloalkyl ring systems are bridged monocyclic rings or fused bicyclic rings.
  • bridged monocyclic rings contain a monocyclic cycloalkyl ring where two non adjacent carbon atoms of the monocyclic ring are linked by an alkylene bridge of between one and three additional carbon atoms (i.e., a bridging group of the form (CH2)w, where w is 1, 2, or 3).
  • bicyclic ring systems include, but are not limited to, bicyclo[3.1.1]heptane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, bicyclo[3.2.2]nonane, bicyclo[3.3.1]nonane, and bicyclo[4.2.1]nonane.
  • fused bicyclic cycloalkyl ring systems contain a monocyclic cycloalkyl ring fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl.
  • the bridged or fused bicyclic cycloalkyl is attached to the parent molecular moiety through any carbon atom contained within the monocyclic cycloalkyl ring.
  • cycloalkyl groups are optionally substituted with one or two groups which are independently oxo or thia.
  • the fused bicyclic cycloalkyl is a 5 or 6 membered monocyclic cycloalkyl ring fused to either a phenyl ring, a 5 or 6 membered monocyclic cycloalkyl, a 5 or 6 membered monocyclic cycloalkenyl, a 5 or 6 membered monocyclic heterocyclyl, or a 5 or 6 membered monocyclic heteroaryl, wherein the fused bicyclic cycloalkyl is optionally substituted by one or two groups which are independently oxo or thia.
  • multicyclic cycloalkyl ring systems are a monocyclic cycloalkyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl.
  • multicyclic cycloalkyl is attached to the parent molecular moiety through any carbon atom contained within the base ring.
  • multicyclic cycloalkyl ring systems are a monocyclic cycloalkyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a monocyclic heteroaryl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl.
  • a cycloalkyl is a cycloalkenyl.
  • the term “cycloalkenyl” is used in accordance with its plain ordinary meaning.
  • a cycloalkenyl is a monocyclic, bicyclic, or a multicyclic cycloalkenyl ring system.
  • monocyclic cycloalkenyl ring systems are cyclic hydrocarbon groups containing from 3 to 8 carbon atoms, where such groups are unsaturated (i.e., containing at least one annular carbon carbon double bond), but not aromatic.
  • monocyclic cycloalkenyl ring systems include cyclopentenyl and cyclohexenyl.
  • bicyclic cycloalkenyl rings are bridged monocyclic rings or a fused bicyclic rings.
  • bridged monocyclic rings contain a monocyclic cycloalkenyl ring where two non adjacent carbon atoms of the monocyclic ring are linked by an alkylene bridge of between one and three additional carbon atoms (i.e., a bridging group of the form (CH2)w, where w is 1, 2, or 3).
  • alkylene bridge of between one and three additional carbon atoms
  • bicyclic cycloalkenyls include, but are not limited to, norbornenyl and bicyclo[2.2.2]oct 2 enyl.
  • fused bicyclic cycloalkenyl ring systems contain a monocyclic cycloalkenyl ring fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocyclyl, or a monocyclic heteroaryl.
  • the bridged or fused bicyclic cycloalkenyl is attached to the parent molecular moiety through any carbon atom contained within the monocyclic cycloalkenyl ring.
  • cycloalkenyl groups are optionally substituted with one or two groups which are independently oxo or thia.
  • multicyclic cycloalkenyl rings contain a monocyclic cycloalkenyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl.
  • the multicyclic cycloalkenyl is attached to the parent molecular moiety through any carbon atom contained within the base ring.
  • multicyclic cycloalkenyl rings contain a monocyclic cycloalkenyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two ring systems independently selected from the group consisting of a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl.
  • the 6 or 7 membered ring contains zero, one or two double bonds and one, two or three heteroatoms selected from the group consisting of O, N, and S.
  • the heterocyclyl monocyclic heterocycle is connected to the parent molecular moiety through any carbon atom or any nitrogen atom contained within the heterocyclyl monocyclic heterocycle.
  • heterocyclyl monocyclic heterocycles include, but are not limited to, azetidinyl, azepanyl, aziridinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiolanyl, 1,3-dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl, isothiazolidinyl, isoxazolinyl, isoxazolidinyl, morpholinyl, oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothienyl
  • the heterocyclyl bicyclic heterocycle is a monocyclic heterocycle fused to either a phenyl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, a monocyclic heterocycle, or a monocyclic heteroaryl.
  • the heterocyclyl bicyclic heterocycle is connected to the parent molecular moiety through any carbon atom or any nitrogen atom contained within the monocyclic heterocycle portion of the bicyclic ring system.
  • bicyclic heterocyclyls include, but are not limited to, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzofuran-3-yl, indolin-1-yl, indolin-2-yl, indolin-3-yl, 2,3-dihydrobenzothien-2-yl, decahydroquinolinyl, decahydroisoquinolinyl, octahydro-1H-indolyl, and octahydrobenzofuranyl.
  • heterocyclyl groups are optionally substituted with one or two groups which are independently oxo or thia.
  • the bicyclic heterocyclyl is a 5 or 6 membered monocyclic heterocyclyl ring fused to a phenyl ring, a 5 or 6 membered monocyclic cycloalkyl, a 5 or 6 membered monocyclic cycloalkenyl, a 5 or 6 membered monocyclic heterocyclyl, or a 5 or 6 membered monocyclic heteroaryl, wherein the bicyclic heterocyclyl is optionally substituted by one or two groups which are independently oxo or thia.
  • Multicyclic heterocyclyl ring systems are a monocyclic heterocyclyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a bicyclic aryl, a monocyclic or bicyclic heteroaryl, a monocyclic or bicyclic cycloalkyl, a monocyclic or bicyclic cycloalkenyl, and a monocyclic or bicyclic heterocyclyl.
  • multicyclic heterocyclyl is attached to the parent molecular moiety through any carbon atom or nitrogen atom contained within the base ring.
  • multicyclic heterocyclyl ring systems are a monocyclic heterocyclyl ring (base ring) fused to either (i) one ring system selected from the group consisting of a bicyclic aryl, a bicyclic heteroaryl, a bicyclic cycloalkyl, a bicyclic cycloalkenyl, and a bicyclic heterocyclyl; or (ii) two other ring systems independently selected from the group consisting of a phenyl, a monocyclic heteroaryl, a monocyclic cycloalkyl, a monocyclic cycloalkenyl, and a monocyclic heterocyclyl.
  • multicyclic heterocyclyl groups include, but are not limited to 10H-phenothiazin-10-yl, 9,10- dihydroacridin-9-yl, 9,10-dihydroacridin-10-yl, 10H-phenoxazin-10-yl, 10,11-dihydro-5H- dibenzo[b,f]azepin-5-yl, 1,2,3,4-tetrahydropyrido[4,3-g]isoquinolin-2-yl, 12H- benzo[b]phenoxazin-12-yl, and dodecahydro-1H-carbazol-9-yl.
  • halo or “halogen,” by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom. Additionally, terms such as “haloalkyl” are meant to include monohaloalkyl and polyhaloalkyl.
  • halo(C1-C4)alkyl includes, but is not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 4-chlorobutyl, 3-bromopropyl, and the like.
  • acyl means, unless otherwise stated, -C(O)R where R is a substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.
  • aryl means, unless otherwise stated, a polyunsaturated, aromatic, hydrocarbon substituent, which can be a single ring or multiple rings (preferably from 1 to 3 rings) that are fused together (i.e., a fused ring aryl) or linked covalently.
  • a fused ring aryl refers to multiple rings fused together wherein at least one of the fused rings is an aryl ring.
  • heteroaryl refers to aryl groups (or rings) that contain at least one heteroatom such as N, O, or S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized.
  • heteroaryl includes fused ring heteroaryl groups (i.e., multiple rings fused together wherein at least one of the fused rings is a heteroaromatic ring).
  • a 5,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 5 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring.
  • a 6,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring.
  • a 6,5- fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 5 members, and wherein at least one ring is a heteroaryl ring.
  • a heteroaryl group can be attached to the remainder of the molecule through a carbon or heteroatom.
  • Non- limiting examples of aryl and heteroaryl groups include phenyl, naphthyl, pyrrolyl, pyrazolyl, pyridazinyl, triazinyl, pyrimidinyl, imidazolyl, pyrazinyl, purinyl, oxazolyl, isoxazolyl, thiazolyl, furyl, thienyl, pyridyl, pyrimidyl, benzothiazolyl, benzoxazoyl benzimidazolyl, benzofuran, isobenzofuranyl, indolyl, isoindolyl, benzothiophenyl, isoquinolyl, quinoxalinyl, quinolyl, 1- naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4- imidazoly
  • Substituents for each of the above noted aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below.
  • a heteroaryl group substituent may be -O- bonded to a ring heteroatom nitrogen.
  • a fused ring heterocyloalkyl-aryl is an aryl fused to a heterocycloalkyl.
  • a fused ring heterocycloalkyl-heteroaryl is a heteroaryl fused to a heterocycloalkyl.
  • a fused ring heterocycloalkyl-cycloalkyl is a heterocycloalkyl fused to a cycloalkyl.
  • a fused ring heterocycloalkyl-heterocycloalkyl is a heterocycloalkyl fused to another heterocycloalkyl.
  • Fused ring heterocycloalkyl-aryl, fused ring heterocycloalkyl-heteroaryl, fused ring heterocycloalkyl- cycloalkyl, or fused ring heterocycloalkyl-heterocycloalkyl may each independently be unsubstituted or substituted with one or more of the substitutents described herein.
  • Spirocyclic rings are two or more rings wherein adjacent rings are attached through a single atom.
  • the individual rings within spirocyclic rings may be identical or different.
  • Individual rings in spirocyclic rings may be substituted or unsubstituted and may have different substituents from other individual rings within a set of spirocyclic rings.
  • Possible substituents for individual rings within spirocyclic rings are the possible substituents for the same ring when not part of spirocyclic rings (e.g., substituents for cycloalkyl or heterocycloalkyl rings).
  • Spirocylic rings may be substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkyl or substituted or unsubstituted heterocycloalkylene and individual rings within a spirocyclic ring group may be any of the immediately previous list, including having all rings of one type (e.g., all rings being substituted heterocycloalkylene wherein each ring may be the same or different substituted heterocycloalkylene).
  • heterocyclic spirocyclic rings means a spirocyclic rings wherein at least one ring is a heterocyclic ring and wherein each ring may be a different ring.
  • substituted spirocyclic rings means that at least one ring is substituted and each substituent may optionally be different.
  • alkylarylene as an arylene moiety covalently bonded to an alkylene moiety (also referred to herein as an alkylene linker).
  • alkylarylene group has the formula: .
  • An alkylarylene moiety may be substituted (e.g., with a substituent group) on the alkylene moiety or the arylene linker (e.g., at carbons 2, 3, 4, or 6) with halogen, oxo, -N 3 , -CF3, -CCl3, -CBr3, -CI3, -CN, -C(O)H, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO2CH3, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , -NHNH 2 , -ONH 2 , -NHC(O)NHNH 2 , substituted or unsubstituted C 1 - C 5 alkyl or substituted or unsubstituted 2 to 5 membered heteroalkyl).
  • alkylarylene is unsubstituted.
  • alkylsulfonyl means a moiety having the formula -S(O2)-R', where R' is a substituted or unsubstituted alkyl group as defined above. R' may have a specified number of carbons (e.g., “C1-C4 alkylsulfonyl”).
  • R' may have a specified number of carbons (e.g., “C1-C4 alkylsulfonyl”).
  • Each of the above terms includes both substituted and unsubstituted forms of the indicated radical.
  • R, R', R'', R'', and R''' each preferably independently refer to hydrogen, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl (e.g., aryl substituted with 1-3 halogens), substituted or unsubstituted heteroaryl, substituted or unsubstituted alkyl, alkoxy, or thioalkoxy groups, or arylalkyl groups.
  • aryl e.g., aryl substituted with 1-3 halogens
  • substituted or unsubstituted heteroaryl substituted or unsubstituted alkyl, alkoxy, or thioalkoxy groups, or arylalkyl groups.
  • each of the R groups is independently selected as are each R', R'', R''', and R''' group when more than one of these groups is present.
  • R' and R'' are attached to the same nitrogen atom, they can be combined with the nitrogen atom to form a 4-, 5-, 6-, or 7-membered ring.
  • -NR'R'' includes, but is not limited to, 1-pyrrolidinyl and 4-morpholinyl.
  • alkyl is meant to include groups including carbon atoms bound to groups other than hydrogen groups, such as haloalkyl (e.g., -CF 3 and -CH 2 CF 3 ) and acyl (e.g., -C(O)CH 3 , -C(O)CF 3 , -C(O)CH 2 OCH 3 , and the like).
  • haloalkyl e.g., -CF 3 and -CH 2 CF 3
  • acyl e.g., -C(O)CH 3 , -C(O)CF 3 , -C(O)CH 2 OCH 3 , and the like.
  • the substituent may be attached to any of the ring atoms (obeying the rules of chemical valency) and in the case of fused rings or spirocyclic rings, a substituent depicted as associated with one member of the fused rings or spirocyclic rings (a floating substituent on a single ring), may be a substituent on any of the fused rings or spirocyclic rings (a floating substituent on multiple rings).
  • the multiple substituents may be on the same atom, same ring, different atoms, different fused rings, different spirocyclic rings, and each substituent may optionally be different.
  • a point of attachment of a ring to the remainder of a molecule is not limited to a single atom (a floating substituent)
  • the attachment point may be any atom of the ring and in the case of a fused ring or spirocyclic ring, any atom of any of the fused rings or spirocyclic rings while obeying the rules of chemical valency.
  • a ring, fused rings, or spirocyclic rings contain one or more ring heteroatoms and the ring, fused rings, or spirocyclic rings are shown with one more floating substituents (including, but not limited to, points of attachment to the remainder of the molecule), the floating substituents may be bonded to the heteroatoms.
  • the ring heteroatoms are shown bound to one or more hydrogens (e.g., a ring nitrogen with two bonds to ring atoms and a third bond to a hydrogen) in the structure or formula with the floating substituent, when the heteroatom is bonded to the floating substituent, the substituent will be understood to replace the hydrogen, while obeying the rules of chemical valency.
  • Two or more substituents may optionally be joined to form aryl, heteroaryl, cycloalkyl, or heterocycloalkyl groups.
  • Such so-called ring-forming substituents are typically, though not necessarily, found attached to a cyclic base structure.
  • the ring-forming substituents are attached to adjacent members of the base structure.
  • two ring-forming substituents attached to adjacent members of a cyclic base structure create a fused ring structure.
  • the ring-forming substituents are attached to a single member of the base structure.
  • two ring-forming substituents attached to a single member of a cyclic base structure create a spirocyclic structure.
  • the ring- forming substituents are attached to non-adjacent members of the base structure.
  • Two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally form a ring of the formula -T-C(O)-(CRR')q-U-, wherein T and U are independently -NR-, -O-, -CRR'-, or a single bond, and q is an integer of from 0 to 3.
  • two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula -A-(CH2)r-B-, wherein A and B are independently -CRR'-, -O-, -NR-, -S-, -S(O) -, -S(O) 2 -, -S(O) 2 NR'-, or a single bond, and r is an integer of from 1 to 4.
  • One of the single bonds of the new ring so formed may optionally be replaced with a double bond.
  • two of the substituents on adjacent atoms of the aryl or heteroaryl ring may optionally be replaced with a substituent of the formula -(CRR') s -X'- (C''R''R'') d -, where s and d are independently integers of from 0 to 3, and X' is -O-, -NR'-, -S-, -S(O)-, -S(O) 2 -, or -S(O) 2 NR'-.
  • R, R', R'', and R''' are preferably independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.
  • heteroatom or “ring heteroatom” are meant to include oxygen (O), nitrogen (N), sulfur (S), phosphorus (P), and silicon (Si).
  • a “substituent group,” as used herein, means a group selected from the following moieties: (A) oxo, halogen, -CCl3, -CBr3, -CF3, -CI3, CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH 2 Br, -CH 2 F, -CH 2 I, -CN, -OH, -NH 2 , -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO2NH2, ⁇ NH2, ⁇ ONH2, ⁇ NHC(O)NHNH2, ⁇ NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -
  • a “size-limited substituent” or “ size-limited substituent group,” as used herein, means a group selected from all of the substituents described above for a “substituent group,” wherein each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C20 alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 20 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C 3 -C 8 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 8 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted C 6 -C 10 aryl, and each substituted or unsubstituted heteroaryl
  • a “lower substituent” or “ lower substituent group,” as used herein, means a group selected from all of the substituents described above for a “substituent group,” wherein each substituted or unsubstituted alkyl is a substituted or unsubstituted C 1 -C 8 alkyl, each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 8 membered heteroalkyl, each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C7 cycloalkyl, each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 7 membered heterocycloalkyl, each substituted or unsubstituted aryl is a substituted or unsubstituted phenyl, and each substituted or unsubstituted heteroaryl is a substituted or unsubstitute
  • each substituted or unsubstituted alkyl may be a substituted or unsubstituted C 1 -C 20 alkyl
  • each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 20 membered heteroalkyl
  • each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3-C8 cycloalkyl
  • each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 8 membered heterocycloalkyl
  • each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C10 aryl
  • each substituted or unsubstituted heteroaryl is a substituted or unsubstituted or unsubstituted
  • each substituted or unsubstituted alkylene is a substituted or unsubstituted C 1 -C 20 alkylene
  • each substituted or unsubstituted heteroalkylene is a substituted or unsubstituted 2 to 20 membered heteroalkylene
  • each substituted or unsubstituted cycloalkylene is a substituted or unsubstituted C 3 -C 8 cycloalkylene
  • each substituted or unsubstituted heterocycloalkylene is a substituted or unsubstituted 3 to 8 membered heterocycloalkylene
  • each substituted or unsubstituted arylene is a substituted or unsubstituted C6-C10 arylene
  • each substituted or unsubstituted heteroarylene is a substituted or unsubstituted 5 to 10 membered heteroarylene.
  • each substituted or unsubstituted alkyl is a substituted or unsubstituted C1-C8 alkyl
  • each substituted or unsubstituted heteroalkyl is a substituted or unsubstituted 2 to 8 membered heteroalkyl
  • each substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C 3 -C 7 cycloalkyl
  • each substituted or unsubstituted heterocycloalkyl is a substituted or unsubstituted 3 to 7 membered heterocycloalkyl
  • each substituted or unsubstituted aryl is a substituted or unsubstituted C6-C10 aryl
  • each substituted or unsubstituted heteroaryl is a substituted or unsubstituted 5 to 9 membered heteroaryl.
  • each substituted or unsubstituted alkylene is a substituted or unsubstituted C1-C8 alkylene
  • each substituted or unsubstituted heteroalkylene is a substituted or unsubstituted 2 to 8 membered heteroalkylene
  • each substituted or unsubstituted cycloalkylene is a substituted or unsubstituted C3-C7 cycloalkylene
  • each substituted or unsubstituted heterocycloalkylene is a substituted or unsubstituted 3 to 7 membered heterocycloalkylene
  • each substituted or unsubstituted arylene is a substituted or unsubstituted C 6 -C 10 arylene
  • each substituted or unsubstituted heteroarylene is a substituted or unsubstituted 5 to 9 membered heteroarylene.
  • a substituted or unsubstituted moiety e.g., substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkylene, substituted or unsubstituted heteroalkylene, substituted or unsubstituted cycloalkylene, substituted or unsubstituted heterocycloalkylene, substituted or unsubstituted arylene, and/or substituted or unsubstituted heteroarylene) is substituted (e.g., is a substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alky
  • a substituted moiety e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene
  • is substituted with at least one substituent group wherein if the substituted moiety is substituted with a plurality of substituent groups, each substituent group may optionally be different. In embodiments, if the substituted moiety is substituted with a plurality of substituent groups, each substituent group is different.
  • a substituted moiety e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene
  • is substituted with at least one size-limited substituent group wherein if the substituted moiety is substituted with a plurality of size-limited substituent groups, each size-limited substituent group may optionally be different.
  • each size-limited substituent group is different.
  • a substituted moiety e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene
  • each lower substituent group is different.
  • a substituted moiety e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, substituted heteroaryl, substituted alkylene, substituted heteroalkylene, substituted cycloalkylene, substituted heterocycloalkylene, substituted arylene, and/or substituted heteroarylene
  • each first substituent group (e.g., R 1.1 , R 2.1 , R 3.1 , R 4.1 , R 5.1 ... R 100.1 ; R 1A.1 , R 2A.1 , R 3A.1 , R 4A.1 , R 5A.1 ... R 100A.1 ; R L1.1 , R L2.1 , R L3.1 , R L4.1 , R L5.1 ... R L100.1 ) may be further substituted with one or more second substituent groups (e.g., R 1.2 , R 2.2 , R 3.2 , R 4.2 , R 5.2 ... R 100.2 ; R 1A.2 , R 2A.2 , R 3A.2 , R 4A.2 , R 5A.2 ... R 100A.2 ; R L1.2 , R L2.2 , R L3.2 , R L4.2 , R L5.2 ... R L100.2 , respectively).
  • each L WW linker may be unsubstituted or independently substituted with one or more first substituent groups, referred to herein as R LWW.1 ; each first substituent group, R LWW.1 , may be unsubstituted or independently substituted with one or more second substituent groups, referred to herein as R LWW.2 ; and each second substituent group may be unsubstituted or independently substituted with one or more third substituent groups, referred to herein as R LWW.3 .
  • Each first substituent group is optionally different.
  • Each second substituent group is optionally different.
  • Each third substituent group is optionally different.
  • R WW is phenyl
  • the said phenyl group is optionally substituted by one or more R WW.1 groups as defined herein below, e.g., when R WW.1 is R WW.2 -substituted or unsubstituted alkyl, examples of groups so formed include but are not limited to itself optionally substituted by 1 or more R WW.2 , which R WW.2 is optionally substituted by one or more R WW.3 .
  • the R WW group is phenyl substituted by R WW.1 , which is methyl
  • the methyl group may be further substituted to form groups including but not limited to:
  • X WW.1 is independently –F, -Cl, -Br, or –I.
  • R WW.2 is independently oxo, halogen, -CX WW.2 3 , -CHX WW.2 2 , -CH 2 X WW.2 , -OCX WW.2 3 , -OCH2X WW.2 , -OCHX WW.2 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ⁇ NH2, ⁇ ONH2, ⁇ NHC(O)NHNH2, ⁇ NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, R WW.3 -substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1
  • R WW.2 is independently oxo, halogen, -CX WW.2 3 , -CHX WW.2 2 , -CH 2 X WW.2 , -OCX WW.2 3 , -OCH 2 X WW.2 , -OCHX WW.2 2 , -CN, -OH, -NH 2 , -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NHNH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -N 3 , unsubstituted alkyl (e.g., C 1 -C 8 , C 1 -C 6 , C 1 -C 4 , or C
  • Each first substituent group is optionally different.
  • Each second substituent group is optionally different.
  • Each third substituent group is optionally different.
  • the “WW” symbol in the R WW.1 , R WW.2 and R WW.3 refers to the designated number of one of the two different R WW substituents.
  • R WW.1 is R 100A.1
  • R WW.2 is R 100A.2
  • R WW.3 is R 100A.3 .
  • R WW.1 is R 100B.1
  • R WW.2 is R 100B.2
  • R WW.3 is R 100B.3 .
  • R WW.1 , R WW.2 and R WW.3 in this paragraph are as defined in the preceding paragraphs.
  • R LWW.1 is independently oxo, halogen, -CX LWW.1 3, -CHX LWW.1 2, -CH2X LWW.1 , -OCX LWW.1 3, -OCH2X LWW.1 , -OCHX LWW.1 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NHNH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -N 3 , R LWW.2 -substituted or unsubstituted alkyl (e.g., C 1 -C 8 , C1-C6, C
  • R LWW.1 is independently oxo, halogen, -CX LWW.1 3, -CHX LWW.1 2, -CH2X LWW.1 , -OCX LWW.1 3, -OCH2X LWW.1 , -OCHX LWW.1 2, -CN, -OH, -NH 2 , -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NHNH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -N 3 , unsubstituted alkyl (e.g., C 1 -C 8 , C 1 -C 6 , C 1 -C 4
  • X LWW.1 is independently –F, -Cl, -Br, or –I.
  • R LWW.2 is independently oxo, halogen, -CX LWW.2 3 , -CHX LWW.2 2 , -CH 2 X LWW.2 , -OCX LWW.2 3, -OCH2X LWW.2 , -OCHX LWW.2 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ⁇ NH2, ⁇ ONH2, ⁇ NHC(O)NHNH2, ⁇ NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -N3, R LWW.3 -substituted or unsubstituted alkyl
  • R LWW.2 is independently oxo, halogen, -CX LWW.2 3 , -CHX LWW.2 2 , -CH 2 X LWW.2 , -OCX LWW.2 3 , -OCH 2 X LWW.2 , -OCHX LWW.2 2 , -CN, -OH, -NH 2 , -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NHNH2, ⁇ NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)-OH, -NHOH, -N3, unsubstituted alkyl (e.g., C 1 -C 8 , C 1 -C 6 , C
  • X LWW.3 is independently –F, -Cl, -Br, or –I.
  • R group R WW group
  • R group is hereby defined as independently oxo, halogen, -CX WW 3, -CHX WW 2, -CH2X WW , -OCX WW 3, -OCH2X WW , -OCHX WW 2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NHNH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -NHOH, -
  • X WW is independently –F, -Cl, -Br, or –I.
  • WW represents the stated superscript number of the subject R group (e.g., 1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.).
  • R WW.1 , R WW.2 , and R WW.3 are as defined above.
  • L group is herein defined as independently a bond, –O-, -NH-, -C(O)-, -C(O)NH-, -NHC(O)-, -NHC(O)NH-, -C(O)O-, -OC(O)-, -S-, -SO2-, -SO2NH-, R LWW.1 -substituted or unsubstituted alkylene (e.g., C1-C8, C1-C6, C1-C4, or C1-C2), R LWW.1 -substituted or unsubstituted heteroalkylene (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, 2 to 3 membered, or 4
  • R LWW.1 represents the stated superscript number of the subject L group (1, 2, 3, 1A, 2A, 3A, 1B, 2B, 3B, etc.).
  • R LWW.1 as well as R LWW.2 and R LWW.3 are as defined above.
  • Certain compounds of the present disclosure possess asymmetric carbon atoms (optical or chiral centers) or double bonds; the enantiomers, racemates, diastereomers, tautomers, geometric isomers, stereoisometric forms that may be defined, in terms of absolute stereochemistry, as (R)-or (S)- or, as (D)- or (L)- for amino acids, and individual isomers are encompassed within the scope of the present disclosure.
  • the compounds of the present disclosure do not include those that are known in art to be too unstable to synthesize and/or isolate.
  • the present disclosure is meant to include compounds in racemic and optically pure forms.
  • Optically active (R)- and (S)-, or (D)- and (L)-isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques.
  • the compounds described herein contain olefinic bonds or other centers of geometric asymmetry, and unless specified otherwise, it is intended that the compounds include both E and Z geometric isomers.
  • the term “isomers” refers to compounds having the same number and kind of atoms, and hence the same molecular weight, but differing in respect to the structural arrangement or configuration of the atoms.
  • the term “tautomer,” as used herein, refers to one of two or more structural isomers which exist in equilibrium and which are readily converted from one isomeric form to another. [0070] It will be apparent to one skilled in the art that certain compounds of this disclosure may exist in tautomeric forms, all such tautomeric forms of the compounds being within the scope of the disclosure.
  • structures depicted herein are also meant to include all stereochemical forms of the structure; i.e., the R and S configurations for each asymmetric center. Therefore, single stereochemical isomers as well as enantiomeric and diastereomeric mixtures of the present compounds are within the scope of the disclosure.
  • structures depicted herein are also meant to include compounds which differ only in the presence of one or more isotopically enriched atoms. For example, compounds having the present structures except for the replacement of a hydrogen by a deuterium or tritium, or the replacement of a carbon by 13 C- or 14 C-enriched carbon are within the scope of this disclosure.
  • the compounds of the present disclosure may also contain unnatural proportions of atomic isotopes at one or more of the atoms that constitute such compounds.
  • the compounds may be radiolabeled with radioactive isotopes, such as for example tritium ( 3 H), iodine-125 ( 125 I), or carbon-14 ( 14 C). All isotopic variations of the compounds of the present disclosure, whether radioactive or not, are encompassed within the scope of the present disclosure.
  • radioactive isotopes such as for example tritium ( 3 H), iodine-125 ( 125 I), or carbon-14 ( 14 C). All isotopic variations of the compounds of the present disclosure, whether radioactive or not, are encompassed within the scope of the present disclosure.
  • each member of the Markush group should be considered separately, thereby comprising another embodiment, and the Markush group is not to be read as a single unit.
  • “Analog” or “analogue” is used in accordance with its plain ordinary meaning within Chemistry and Biology and refers to a chemical compound that is structurally similar to another compound (i.e., a so-called “reference” compound) but differs in composition, e.g., in the replacement of one atom by an atom of a different element, or in the presence of a particular functional group, or the replacement of one functional group by another functional group, or the absolute stereochemistry of one or more chiral centers of the reference compound.
  • an analog is a compound that is similar or comparable in function and appearance but not in structure or origin to a reference compound.
  • the terms “a” or “an”, as used in herein means one or more.
  • the phrase “substituted with a[n]”, as used herein, means the specified group may be substituted with one or more of any or all of the named substituents.
  • a group such as an alkyl or heteroaryl group
  • the group may contain one or more unsubstituted C1-C20 alkyls, and/or one or more unsubstituted 2 to 20 membered heteroalkyls.
  • R substituent the group may be referred to as “R-substituted.” Where a moiety is R-substituted, the moiety is substituted with at least one R substituent and each R substituent is optionally different.
  • each R 13 substituent may be distinguished as R 13A , R 13B , R 13C , R 13D , etc., wherein each of R 13A , R 13B , R 13C , R 13D , etc. is defined within the scope of the definition of R 13 and optionally differently.
  • Paramagnetic ions that may be used as additional imaging agents in accordance with the embodiments of the disclosure include, but are not limited to, ions of transition and lanthanide metals (e.g., metals having atomic numbers of 21-29, 42, 43, 44, or 57-71). These metals include ions of Cr, V, Mn, Fe, Co, Ni, Cu, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. [0079] Descriptions of compounds of the present disclosure are limited by principles of chemical bonding known to those skilled in the art.
  • a group may be substituted by one or more of a number of substituents
  • substitutions are selected so as to comply with principles of chemical bonding and to give compounds which are not inherently unstable and/or would be known to one of ordinary skill in the art as likely to be unstable under ambient conditions, such as aqueous, neutral, and several known physiological conditions.
  • a heterocycloalkyl or heteroaryl is attached to the remainder of the molecule via a ring heteroatom in compliance with principles of chemical bonding known to those skilled in the art thereby avoiding inherently unstable compounds.
  • the term “leaving group” is used in accordance with its ordinary meaning in chemistry and refers to a moiety (e.g., atom, functional group, molecule) that separates from the molecule following a chemical reaction (e.g., bond formation, reductive elimination, condensation, cross- coupling reaction) involving an atom or chemical moiety to which the leaving group is attached, also referred to herein as the “leaving group reactive moiety”, and a complementary reactive moiety (i.e. a chemical moiety that reacts with the leaving group reactive moiety) to form a new bond between the remnants of the leaving groups reactive moiety and the complementary reactive moiety.
  • a chemical reaction e.g., bond formation, reductive elimination, condensation, cross- coupling reaction
  • a complementary reactive moiety i.e. a chemical moiety that reacts with the leaving group reactive moiety
  • Non limiting examples of leaving groups include hydrogen, hydroxide, organotin moieties (e.g., organotin heteroalkyl), halogen (e.g., Br), perfluoroalkylsulfonates (e.g. triflate), tosylates, mesylates, water, alcohols, nitrate, phosphate, thioether, amines, ammonia, fluoride, carboxylate, phenoxides, boronic acid, boronate esters, and alkoxides.
  • organotin moieties e.g., organotin heteroalkyl
  • halogen e.g., Br
  • perfluoroalkylsulfonates e.g. triflate
  • tosylates mesylates, water, alcohols, nitrate, phosphate, thioether, amines, ammonia, fluoride, carboxylate, phenoxides, boronic
  • two molecules with leaving groups are allowed to contact, and upon a reaction and/or bond formation (e.g., acyloin condensation, aldol condensation, Claisen condensation, Stille reaction) the leaving groups separates from the respective molecule.
  • a reaction and/or bond formation e.g., acyloin condensation, aldol condensation, Claisen condensation, Stille reaction
  • the leaving groups separates from the respective molecule.
  • variable of a compound as described herein when a variable of a compound as described herein is connected (e.g., bonded) to the remainder of the compound through a single bond, that variable is understood to represent a monovalent form (i.e., capable of forming a single bond due to an unfilled valence) of a standalone compound (e.g., if the variable is named “methane” in an embodiment but the variable is known to be attached by a single bond to the remainder of the compound, a person of ordinary skill in the art would understand that the variable is actually a monovalent form of methane, i.e., methyl or –CH 3 ).
  • variable is the divalent form of a standalone compound (e.g., if the variable is assigned to “PEG” or “polyethylene glycol” in an embodiment but the variable is connected by two separate bonds to the remainder of the compound, a person of ordinary skill in the art would understand that the variable is a divalent (i.e., capable of forming two bonds through two unfilled valences) form of PEG instead of the standalone compound PEG).
  • salt refers to acid or base salts of the compounds used in the methods of the present invention.
  • Illustrative examples of acceptable salts are mineral acid (hydrochloric acid, hydrobromic acid, phosphoric acid, and the like) salts, organic acid (acetic acid, propionic acid, glutamic acid, citric acid and the like) salts, quaternary ammonium (methyl iodide, ethyl iodide, and the like) salts.
  • the compounds of the present disclosure may exist as salts.
  • the present disclosure includes such salts.
  • the neutral forms of the compounds are preferably regenerated by contacting the salt with a base or acid and isolating the parent compound in the conventional manner.
  • the parent form of the compound may differ from the various salt forms in certain physical properties, such as solubility in polar solvents.
  • Certain compounds of the present disclosure can exist in unsolvated forms as well as solvated forms, including hydrated forms. In general, the solvated forms are equivalent to unsolvated forms and are encompassed within the scope of the present disclosure. Certain compounds of the present disclosure may exist in multiple crystalline or amorphous forms. In general, all physical forms are equivalent for the uses contemplated by the present disclosure and are intended to be within the scope of the present disclosure.
  • the term “about” means a range of values including the specified value, which a person of ordinary skill in the art would consider reasonably similar to the specified value. In embodiments, about means within a standard deviation using measurements generally acceptable in the art. In embodiments, about means a range extending to +/- 10% of the specified value. In embodiments, about includes the specified value. [0087] “Contacting” is used in accordance with its plain ordinary meaning and refers to the process of allowing at least two distinct species (e.g., chemical compounds including biomolecules or cells) to become sufficiently proximal to react, interact or physically touch.
  • the resulting reaction product can be produced directly from a reaction between the added reagents or from an intermediate from one or more of the added reagents that can be produced in the reaction mixture.
  • “comprises,” “comprising,” “containing” and “having” and the like can have the meaning ascribed to them in U.S. Patent law and can mean “ includes,” “including,” and the like. “Consisting essentially of” or “consists essentially” likewise has the meaning ascribed in U.S.
  • polymer is used in accordance with its plain ordinary meaning in the art, and refers to a molecule including repeating subunits (e.g., polymerized monomers).
  • dehydrogenated polymer refers to a polymer including a carbon-carbon double bond.
  • olefin metathesis is used in accordance with its plain ordinary meaning in the art, and refers to an organic reaction involving the redistribution of fragments of alkenes (olefins) by the scission and regeranation of carbon-carbon double bonds.
  • olefin isomerization is used in accordance with its plain ordinary meaning in the art, and refers to an organic reaction involving the relocation of a carbon-carbon double bond in a molecule to a different part of the molecule. In embodiments, olefin isomerization is isomerization of a terminal olefin to an internal olefin.
  • dehydrogenation is used in accordance with its plain ordinary meaning in the art, and refers to an organic reaction involving the removal of hydrogen, e.g., from an organic molecule. In embodiments, dehydrogenation is the conversion of an alkane to an olefin.
  • catalyst is used in accordance with its plain ordinary meaning in the art, and refers to a species that increases the rate of a chemical reaction. The catalyst is not consumed in the reaction and can continue to act repeatedly.
  • high-density polyethylene or “HDPE” refers to a thermoplastic polymer produced from the monomer ethylene and is known for its high strength-to-density ratio.
  • the density of HDPE ranges from about 0.93 g/cm 3 to about 0.97 g/cm 3 .
  • HDPE has minimal branching of its polymer chains and is therefore denser than low-density polyethylene.
  • low-density polyethylene or “LDPE” refers to a thermoplastic polymer produced from the monomer ethylene.
  • the density of LDPE ranges from about 0.917 g/cm 3 to about 0.930 g/cm 3 .
  • linear low-density polyethylene or “LLDPE” refers to a substantially linear polyethylene with significant numbers of short branches. LLDPE differs from LDPE because of the absence of long chain branching.
  • the density of LLDPE ranges from about 0.91 g/cm 3 to about 0.94 g/cm 3 .
  • Methods [0098] In an aspect is provided a method of degrading a substance, the method including: (i) conducting one or more reaction(s) to form one or more olefin units in the substance; (ii) subjecting, after step (i), to conditions for olefin metathesis; and (iii) subjecting, after step (i), to conditions for olefin isomerization. In embodiments, step (i) includes subjecting the substance to conditions for dehydrogenation.
  • a method of making a substituted or unsubstituted alkene including subjecting a dehydrogenated polymer to conditions for olefin metathesis and to conditions for olefin isomerization.
  • a method of making a substituted or unsubstituted alkene comprising subjecting a first substance to conditions for olefin metathesis and to conditions for olefin isomerization; wherein: (i) the first substance includes at most 10% unsaturated alkene monomer units; (ii) the first substance includes at least 20 carbon atoms per molecule; or (iii) prior to subjecting the first substance to conditions for olefin metathesis and to conditions for olefin isomerization, the method includes subjecting a second substance to conditions for dehydrogenation, thereby forming the first substance.
  • the subjecting to conditions for olefin metathesis and subjecting to conditions for olefin isomerization are conducted simultaneously. In embodiments, the subjecting to conditions for olefin metathesis and subjecting to conditions for olefin isomerization are conducted simultaneously via orthogonal tandem catalysis.
  • the substance includes one or more polymers. In embodiments, the substance includes one polymer. In embodiments, the substance includes multiple polymers. In embodiments, the substance includes one or more polyolefins. In embodiments, the substance includes one polyolefin. In embodiments, the substance includes multiple polyolefins. In embodiments, the substance is a polyolefin.
  • the substance includes one or more polymers including one or more monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, vinyl chloride units, vinyl fluoride units, cyclopentene units, cyclohexene units, cycloheptene units, cyclooctene units, cyclononane units, cyclodecene units, cycloundecene units, cyclododecene, and norbornene units.
  • monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-hexen
  • the substance includes one or more monomer units selected from ethylene, propene, styrene, and vinyl chloride. In embodiments, the substance includes one or more monomer units selected from ethylene and propene. In embodiments, the substance includes one or more monomer units selected from ethylene.
  • the substance includes one or more co-polymers including one or more monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, vinyl chloride units, vinyl fluoride units, cyclopentene units, cyclohexene units, cycloheptene units, cyclooctene units, cyclononane units, cyclodecene units, cycloundecene units, cyclododecene, and norbornene units.
  • monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-
  • the substance includes one or more co-polymers including one or more monomer units selected from ethylene units, propene units, 1-butene units, 2-butene units, isobutene units, 1-pentene units, 2-pentene units, 1-hexene units, 2-hexene units, 3-hexene units, 1-heptene units, 1-octene units, 1-nonene units, 1-decene units, styrene units, and vinyl chloride units.
  • the substance includes one or more co-polymers including one or more monomer units selected from ethylene units, propene units, styrene units, and vinyl chloride units.
  • the substance includes one or more co-polymers including one or more monomer units selected from ethylene units and propene units. In embodiments, the substance includes one or more co-polymers including one or more monomer units selected from ethylene units. [0106] In embodiments, the substance includes one or more block co-polymers including one or more blocks selected from polyethylene block(s), polypropylene block(s), poly(vinyl chloride) block(s), polybutene block(s), polyisobutene block(s), poly(1-butene) block(s), poly(2-butene) block(s), polypentene block(s), poly(4-methyl-1-pentene) block(s), polystyrene block(s), poly(cyclopentene) block(s), poly(cyclohexene) block(s), poly(cycloheptene) block(s), poly(cyclooctene) block(s), poly(cyclononene) block(s), poly(cyclode
  • the substance includes one or more block co-polymers including one or more blocks selected from polyethylene block(s), polypropylene block(s), poly(vinyl chloride) block(s), polyisobutene block(s), poly(4-methyl-1-pentene) block(s), polystyrene block(s), and poly(cyclooctene) block(s).
  • the substance includes one or more block co-polmers including one or more blocks selected from polyethylene block(s), polypropylene block(s), poly(vinyl chloride) block(s), and polystyrene block(s).
  • the substance includes one or more block co-polymers including one or more blocks selected from polyethylene block(s) and polypropylene block(s). In embodiments, the substance includes one or more block co-polymers including one or more blocks selected from polyethylene block(s). [0107] In embodiments, the substance includes one or more homopolymers selected from polyethylene, polypropylene, polystyrene, poly(vinyl chloride), polybutene, polyisobutene, polybutene, poly(1-butene), poly(2-butene), polyisobutylene, polypentene, poly(4-methyl-1- pentene), polystyrene, and poly(vinyl chloride). In embodiments, the substance includes polyethylene.
  • the substance is polyethylene. In embodiments, the substance includes waste polyethylene. In embodiments, the substance includes one or more polyethylenes. In embodiments, the substance is one or more polyethylenes. In embodiments, the substance includes one or more polyethylene(s) selected from high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and co-polymers thereof. In embodiments, the substance includes one or more polyethylene(s) selected from high-density polyethylene, low-density polyethylene, and co-polymers thereof. In embodiments, the substance includes one or more polyethylene(s) selected from high-density polyethylene and low-density polyethylene. In embodiments, the substance includes high-density polyethylene.
  • the substance includes low-density polyethylene. In embodiments, the substance includes linear low-density polyethylene. In embodiments, the substance is high- density polyethylene. In embodiments, the substance is low-density polyethylene. In embodiments, the substance is linear low-density polyethylene. [0108] In embodiments, the substance includes polypropylene. In embodiments, the substance includes syndiotactic polypropylene. In embodiments, the substance includes atactic polypropylene. In embodiments, the substance includes isotactic polypropylene. [0109] In embodiments, the substance includes plastic waste.
  • the substance includes plastic waste selected from milk jugs, shampoo bottles, lawn chairs, food containers, trash bags, barrels, drainage pipes, grocery bags, and cereal box liners.
  • the formation of one or more olefin units in the substance includes subjecting the substance to conditions for dehydrogenation.
  • the formation of one or more olefin units in the substance includes conducting on the substance one or more dehydrogenation reactions.
  • the one or more dehydrogenation reactions include one or more reactions including removal of one or more proton-hydride pairs, wherein each of the one or more proton-hydride pairs includes one proton and one hydride.
  • the one or more dehydrogenation reactions transform a reactant into a dehydrogenated substance.
  • the one or more dehydrogenation reactions include one or more acceptorless dehydrogenation reactions.
  • the one or more dehydrogenation reactions include one or more transfer dehydrogenation reactions.
  • the one or more dehydrogenation reactions include one or more transfer dehydrogenation reactions that include treatment of the substance with one or more hydrogen acceptors.
  • the one or more dehydrogenation reactions include one or more oxidative dehydrogenation reactions.
  • the one or more dehydrogenation reactions include treatment of the substance with one or more hydrogen acceptors.
  • the one or more dehydrogenation reactions produce a dehydrogenated substance.
  • the dehydrogenated substance is purified. In embodiments, the dehydrogenated substance is purified via one or more techniques selected from distillation or precipitation from one or more organic solvents, or precipitation from water. [0111]
  • the one or more transfer dehydrogenation reactions include treatment with one or more hydrogen acceptors selected from ethylene, propylene, butene, tert- butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O 2 , CO 2 , CO, optionally substituted benzoquinone, and N2.
  • the one or more hydrogen acceptors is indepdently selected from ethylene, propylene, butene, tert-butylethylene, norbornene, norbornadiene, butadiene, and styrene.
  • the one or more hydrogen acceptors is independently selected from ethylene, propylene, tert-butylethylene, norbornene, and norbornadiene. In embodiments, the one or more hydrogen acceptors is independently selected from ethylene, propylene, tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from ethylene, tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from tert-butylethylene, and norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from tert-butylethylene and norbornene.
  • the one or more hydrogen acceptors is independently selected from norbornene. In embodiments, the one or more hydrogen acceptors is independently selected from tert-butylethylene. In embodiments, the one or more hydrogen acceptors is ethylene. In embodiments, the one or more hydrogen acceptors is propene. [0113] In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 20 to 1000 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 50 to 500 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 100 to 400 °C.
  • the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 100 to 300 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at temperatures ranging from 100 to 200 °C. In embodiments, the dehydrogenation is conducted at a temperature of at least 20 °C, at least 50 °C, at least 65 °C, at least 80 °C, at least 100 ° C, at least 120 °C, at least 200 °C, at least 250 °C, at least 300 °C, at least 350 °C, at least 400 °C, at least 500 °C, at least 600 °C, at least 1000 °C, or more.
  • the dehydrogenation is conducted at a temperature of at most 20 °C, at most 50 °C, at most 65 °C, at most 80 °C, at most 100 ° C, at most 120 °C, at most 200 °C, at most 250 °C, at most 300 °C, at most 350 °C, at most 400 °C, at most 500 °C, at most 600 °C, at most 1000 °C, or less.
  • the conditions for dehydrogenation include conducting one or more reactions at a temperature of about 20 °C to about 1000 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at a temperature of at least about 20 °C.
  • the conditions for dehydrogenation include conducting one or more reactions at a temperature of at most about 1000 °C. In embodiments, the conditions for dehydrogenation include conducting one or more reactions at a temperature of about 20 °C to about 65 °C, about 20 °C to about 100 °C, about 20 °C to about 150 °C, about 20 °C to about 200 °C, about 20 °C to about 300 °C, about 20 °C to about 350 °C, about 20 °C to about 400 °C, about 20 °C to about 450 °C, about 20 °C to about 500 °C, about 20 °C to about 600 °C, about 20 °C to about 1000 °C, about 65 °C to about 100 °C, about 65 °C to about 150 °C, about 65 °C to about 200 °C, about 65 °C to about 300 °C, about 65 °C to about 350 °C, about 65 °C to about 400 °
  • the conditions for dehydrogenation include conducting one or more reactions at a temperature of about 20 °C, about 65 °C, about 100 °C, about 150 °C, about 200 °C, about 300 °C, about 350 °C, about 400 °C, about 450 °C, about 500 °C, about 600 °C, or about 1000 °C.
  • the conditions for dehydrogenation include subjecting a neat substance to one or more dehydrogenation reaction(s).
  • the conditions for dehydrogenation include melting the substance.
  • the conditions for dehydrogenation include melting the polymer.
  • the conditions for dehydrogenation include melting the polyethylene.
  • the conditions for dehydrogenation include contacting a substance with one or more solvents selected from benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, octane, octanes, nonane, nonanes, decane, decanes, undecane, undecanes, dodecane, and dodecanes.
  • benzene e.g
  • the conditions for dehydrogenation include contacting a substance with a mixture of multiple organic solvents.
  • the conditions for dehydrogenation include conducting a batch reaction.
  • the conditions for dehydrogenation include flowing one or more gases over the headspace of a batch reaction.
  • the conditions for dehydrogenation include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction.
  • the conditions for dehydrogenation include contacting a substance with one or more dehydrogenation catalysts.
  • the one or more dehydrogenation catalysts includes a homogeneous catalyst.
  • the one or more dehydrogenation catalysts includes a heterogeneous catalyst. In embodiments, the one or more dehydrogenation catalysts is (are) immobilized. [0119] In embodiments, the formation of one or more olefin units in the substance includes subjecting the substance to conditions for cracking. In embodiments, the (i) conducting one or more reaction(s) to form one or more olefin units in the substance includes subjecting the substance to conditions for cracking. In embodiments, the cracking is thermal cracking. In embodiments, the cracking is catalytic cracking. In embodiments, the cracking is fluid catalytic cracking. In embodiments, the cracking includes hydrocracking.
  • the conditions for cracking include heating to a temperature of 100 °C to 900 °C. In embodiments, the conditions for cracking include heating to a temperature of 300 °C to 700 °C. In embodiments, the conditions for cracking include heating to a temperature of 300 °C to 600 °C. In embodiments, the conditions for cracking include heating to a temperature of 400 °C to 650 °C. In embodiments, the conditions for cracking include treatment with one or more catalysts selected from alumina, silica, zeolite X, and zeolite Y. In embodiments, the conditions for cracking include selectively forming olefins from paraffins.
  • the conditions for cracking include selectively forming monoenes or nonconjugated dienes from paraffins. In embodiments, the conditions for cracking include selectively forming monoenes from paraffins.
  • the formation of one or more olefin units includes a polymerization. In embodiments, the polymerization includes termination of chain growth. In embodiments, the polymerization includes termination of chain growth to release one or more olefin units. In embodiments, the termination of chain growth includes ⁇ -hydride elimination. In embodiments, the termination of chain growth includes chain-transfer to monomer.
  • the formation of one or more olefin units includes a polymerization of one or more monomer units or co-monomer units including two or more degrees of unsaturation.
  • the one or more monomer units co-monomer units including two or more degrees of unsaturation is a polyene (e.g., diene) or alkyne.
  • the one or more monomer units co-monomer units including two or more degrees of unsaturation is selected from butadiene, acetylene, and norbornadiene.
  • the formation of one or more olefin units includes post-polymerization modification.
  • the post-polymerization modification includes one or more reaction sequences selected from (i) C-H olefination; (ii) C-H functionalization to install a heteroatom, X, followed by elimination of HX; (iii) CH formylation to install an aldehyde followed by Wittig coupling; (iv) CH carboxylation to install an ester followed by treatment with Tebbe’s reagent or Petasis reagent; (v) Julia olefination; and (vi) CH alkynylation to install one or more alkynes followed by reduction of the one or more alkynes to alkenes.
  • reaction sequences selected from (i) C-H olefination; (ii) C-H functionalization to install a heteroatom, X, followed by elimination of HX; (iii) CH formylation to install an aldehyde followed by Wittig coupling; (iv) CH carboxylation to install an ester followed by treatment with Tebbe’s
  • the post-polymerization modification includes C-H functionalization to install a heteroatom, X, followed by elimination of HX. In embodiments, the post-polymerization modification includes C-H halogenation, followed by elimination. In embodiments, the post-polymerization modification includes C-H halogenation, followed by base-promoted elimination. [0122] In embodiments, the formation of one or more olefin units includes installation of a leaving group on a substance. In embodiments, the formation of one or more olefin units includes installation of a leaving group on a substance and elimination of the leaving group.
  • the leaving group is selected from -F, -Cl, -Br, -I, -OTf, -OTs, -OMs, -(OR2) + , - (NR3) + , OC(O)R, OC(O)OR, OC(O)X, and SO2R, wherein R and X are independently selected from H, substituted or unsubstituted C 1- C 30 alkyl, and 3 to 10 membered heterocycloalkyl.
  • the leaving group is selected from -F, -Cl, -Br, and -I.
  • the leaving group is selected from -Cl, -Br, and -I.
  • the method further includes a pre-metathesis step conducted after the (i) forming one or more olefins, before the (ii) subjecting to conditions for olefin metathesis, and before the (iii) subjecting to conditions for olefin isomerization.
  • the pre- metathesis step includes treating with one or more olefin metathesis catalysts.
  • the pre-metathesis step includes treating with one or more olefins.
  • the pre- metathesis step includes treating with ethylene.
  • the pre-metathesis step includes treating with ethylene and one or more olefin metathesis catalysts.
  • the conditions for olefin metathesis include treatment with one or more olefins. In embodiments, the conditions for olefin metathesis include treatment with one or more exogenously added olefins. In embodiments, the conditions for olefin metathesis include treatment with 0.1-1000 equiv of the one or more olefins. In embodiments, the conditions for olefin metathesis include treatment with one or more olefins independently selected from C 2- C 40 olefins. In embodiments, the conditions for olefin metathesis include treatment with an optionally substituted C2 olefin.
  • the conditions for olefin metathesis include treatment with one or more olefins independently selected from ethylene, propylene, 1-butene, 2- butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-hepene, 1- octene, 2-octene, 3-octene, 4-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene, 1-decene, 2- decene, 3-decene, 4-decene, 5-decene, 1-undecene, 2-undecene, 3-undecene, 4-undecene, 5- undecene, 1-dodecene, 2-dodecene, 3-dodecene, 4-dodecene, 5-dodecene, 6-dodecene, 1- tride
  • the one or more olefins include one or more gaseous olefins.
  • the conditions for olefin metathesis include treatment with 0.1-1000 bar of the one or more gaseous olefins.
  • the conditions for olefin metathesis include treatment with 5-100 bar of the one or more gaseous olefins.
  • the conditions for olefin metathesis include treatment with 10-100 bar of the one or more gaseous olefins.
  • the conditions for olefin metathesis include treatment with ethylene.
  • the conditions for olefin metathesis include treatment with ethylene in a pressure of 0.1-1000 bar.
  • the conditions for olefin metathesis include conditions for ethenolysis. In embodiments, the conditions for olefin metathesis include treatment with propylene. In embodiments, the conditions for olefin metathesis include treatment with propylene in a pressure of 0.1-1000 bar. In embodiments, the conditions for olefin metathesis include conditions for propenolysis. In embodiments, the conditions for olefin metathesis include treatment with butenes. In embodiments, the conditions for olefin metathesis include treatment with butenes in a pressure of 0.1-1000 bar. In embodiments, the conditions for olefin metathesis include conditions for butenolysis.
  • the conditions for olefin metathesis include treatment with 2-butene. In embodiments, the conditions for olefin metathesis include treatment with 2-butene in a pressure of 0.1-1000 bar. In embodiments, the conditions for olefin metathesis include conditions for 2-butenolysis. In embodiments, the conditions for olefin metathesis include treatment with ethylene and one or more olefin metathesis catalysts. [0126] In embodiments, the conditions for olefin metathesis include heating at 20-500 °C. In embodiments, the conditions for olefin metathesis include heating at 20-200 °C. In embodiments, the conditions for olefin metathesis include heating at 40-170 °C.
  • the conditions for olefin metathesis include heating at 40-160 °C. In embodiments, the conditions for olefin metathesis include heating at 140-170 °C. In embodiments, the conditions for olefin metathesis include heating at 40-100 °C. [0127] In embodiments, a neat substance is subjected to the conditions for olefin metathesis. In embodiments, the conditions for olefin metathesis include melting the dehydrogenated substance. In embodiments, the conditions for olefin metathesis include melting a polymer. In embodiments, the conditions for olefin metathesis include contacting a substance with one or more solvents.
  • the conditions for olefin metathesis include contacting a substance with one or more organic solvents. In embodiments, the conditions for olefin metathesis include contacting a substance with one or more hydrocarbon solvents. In embodimetns, the conditions for olefin metathesis include contacting a substance with one or more solvents selected from benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, h
  • the conditions for olefin metathesis include conducting a batch reaction. In embodiments, the conditions for olefin metathesis include flowing one or more gases over the headspace of a batch reaction. In embodiments, the conditions for olefin metathesis include conducting a continuous-flow reaction. In embodiments, the conditions for olefin metathesis include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction. [0129] In embodiments, the conditions for olefin metathesis include contacting the substance with one or more olefin metathesis catalysts. In embodiments, the one or more olefin metathesis catalysts include one or more homogeneous catalyst(s).
  • the one or more olefin metathesis catalysts include one or more heterogeneous catalyst(s). In embodiments, one or more of the one or more olefin metathesis catalysts is (are) immobilized. In embodiments, the one or more olefin metathesis catalyst(s) is/are selected from Schrock-type olefin metathesis catalyst(s), Grubbs-type olefin metathesis catalyst(s), Hoveyda/Grubbs-type olefin metathesis catalyst(s), and heterogenous-type olefin metathesis catalyst(s). In embodiments, the one or more olefin metathesis catalysts includes Hoveyda Grubbs II.
  • the one or more olefin metathesis catalysts is Hoveyda Grubbs II. In embodiments, the one or more olefin metathesis catalysts includes Ultra-Nitro-Cat. In embodiments, the one or more olefin metathesis catalysts includes Re2O7. In embodiments, the one or more olefin metathesis catalysts includes Re2O7 on alumina. In embodiments, the one or more olefin metathesis catalysts includes Re 2 O 7 on silica. In embodiments, the one or more olefin metathesis catalysts includes Re 2 O 7 on a zeolite. In embodiments, the one or more olefin metathesis catalysts includes Re2O7 on zeolite Y.
  • the one or more olefin metathesis catalysts includes tungsten.
  • the conditions for olefin metathesis include conducting more than one metathesis reaction conducted per molecule present in the substance.
  • the conditions for olefin metathesis include conducting more than one nondegenerate metathesis reaction conducted per molecule present in the substance.
  • the conditions for olefin metathesis include conducting 2-100,000 nondegenerate metathesis reactions per molecule present in the substance.
  • the conditions for olefin isomerization include conditions for positional olefin isomerization.
  • the conditions for olefin isomerization include conditions for positional, long-range olefin isomerization. In embodiments, the conditions for olefin isomerization include conditions for positional, short-range olefin isomerization. In embodiments, the conditions for olefin isomerization include conditions for isomerization of terminal olefins to internal olefins.
  • the conditions for olefin isomerization include conducting one or more olefin isomerization(s) proceeding through one or more intermediate(s) independently selected from metal-hydride intermediate(s), metal-allyl intermediate(s), cationic intermediate(s), carbocationic intermediate(s), anionic intermediate(s), carbanionic intermediate(s), radical intermediate(s), metal-radical intermediate(s), radical cationic intermediate(s), and radical anionic intermediate(s).
  • the one or more olefin isomerization(s) proceed(s) through one or more metal-hydride intermediate(s).
  • the one or more olefin isomerization(s) proceed(s) through one or more metal- allyl intermediate(s).
  • the one or more olefin isomerization(s) proceed(s) through one or more cationic intermediate(s).
  • the conditions for olefin isomerization include heating at 20 °C to 1000 °C. In embodiments, the conditions for olefin isomerization include heating at 20 °C to 200 °C. In embodiments, the conditions for olefin isomerization include heating at 20 °C to 175 °C.
  • a neat substance is subjected to the conditions for olefin isomerization. In embodiments, the conditions for olefin isomerization include melting the dehydrogenated substance.
  • the conditions for olefin isomerization include melting the polymer. In embodiments, the conditions for olefin isomerization include contacting a substance with one or more solvents. In embodiments, the conditions for olefin isomerization include contacting a substance with one or more solvents selected from benzene, toluene, o- xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, heptanes, o
  • the conditions for olefin isomerization include treatment with one or more bases.
  • the conditions for olefin isomerization include contacting a substance with one or more olefin isomerization catalysts.
  • the one or more olefin isomerization catalysts include a homogeneous catalyst.
  • the one or more olefin isomerization catalysts include a heterogeneous catalyst.
  • the one or more olefin isomerization catalysts include an immobilized catalyst.
  • the conditions for olefin isomerization include treatment with one or more olefin isomerization catalysts.
  • the conditions for olefin isomerization include treatment with one or more homogeneous olefin isomerization catalysts. In embodiments, the conditions for olefin isomerization include treatment with one or more heterogeneous olefin isomerization catalysts. [0135] In embodiments, the conditions for olefin isomerization include conducting a batch reaction. In embodiments, the conditions for olefin isomerization include flowing one or more gases over the headspace of a batch reaction. In embodiments, the conditions for olefin isomerization include conducting a continuous-flow reaction.
  • the conditions for olefin isomerization include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction.
  • the (b) subjecting to conditions for olefin metathesis and the (c) subjecting to conditions for olefin isomerization are collectively conducted as an isomerizing olefin metathesis.
  • the one or more olefins formed in the (a) forming one or more olefins is subjected to an isomerizing olefin metathesis.
  • the isomerizing olefin metathesis includes an isomerizing ethenolysis.
  • the isomerizing olefin metathesis is an isomerizing ethenolysis.
  • the isomerizing olefin metathesis includes repetition of a cycle including (i) olefin metathesis and (ii) olefin isomerization.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1- 500,000 times.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-200,000 times.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-100,000 times.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-50,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1- 5,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 500 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated 1-50 times.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated at least 1 time, at least 50 times, at least 100 times, at least 500 times, at least 2000 times, at least 10,000 times, at least 50,000 times, at least 100,000 times, at least 500,000 or more.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated at most 1 time, at most 50 times, at most 100 times, at most 500 times, at most 2000 times, at most 10,000 times, at most 50,000 times, at most 100,000 times, at most 500,000 or less.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time to about 500,000 times. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated at least about 1 time. In embodiments, the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated at most about 500,000 times.
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time to about 50 times, about 1 time to about 100 times, about 1 time to about 500 times, about 1 time to about 1,000 times, about 1 time to about 5,000 times, about 1 time to about 10,000 times, about 1 time to about 25,000 times, about 1 time to about 50,000 times, about 1 time to about 100,000 times, about 1 time to about 250,000 times, about 1 time to about 500,000 times, about 50 times to about 100 times, about 50 times to about 500 times, about 50 times to about 1,000 times, about 50 times to about 5,000 times, about 50 times to about 10,000 times, about 50 times to about 25,000 times, about 50 times to about 50,000 times, about 50 times to about 100,000 times, about 50 times to about 250,000 times, about 50 times to about 500,000 times, about 100 times to about 500 times, about 100 times to about 1,000 times, about 100 times to about 5,000 times, about 100 times to about 10,000 times, about 100 times to about 25,000 times, about 100 times to about
  • the cycle including (i) olefin metathesis and (ii) olefin isomerization is repeated about 1 time, about 50 times, about 100 times, about 500 times, about 1,000 times, about 5,000 times, about 10,000 times, about 25,000 times, about 50,000 times, about 100,000 times, about 250,000 times, or about 500,000 times.
  • the isomerizing olefin metathesis is conducted at 20-500 °C.
  • a neat substance is subjected to the conditions for isomerizing olefin metathesis.
  • the conditions for isomerizing olefin metathesis include melting the dehydrogenated substance.
  • the conditions for isomerizing olefin metathesis include melting a polymer. In embodiments, the conditions for isomerizing olefin metathesis include contacting a substance with one or more solvents. In embodiments, the conditions for isomerizing olefin metathesis include contacting a substance with one or more solvents selected from benzene, toluene, o-xylene, m-xylene, p-xylene, dichlorobenzene (e.g., o-dichlorobenzene), trichlorobenzene (e.g., 1,2,4-trichlorobenzene), dioxane, tetrahydrofuran, tetrahydropyran, acetone, chloroform, carbon tetrachloride, dichloromethane, ethyl acetate, pentane, pentanes, hexane, hexanes, heptane, h
  • the conditions for isomerizing olefin metathesis include treatment with one or more bases.
  • the conditions for isomerizing olefin metathesis include contacting a substance with one or more olefin metathesis catalysts.
  • one or more of the one or more olefin metathesis catalysts is capable of olefin isomerization.
  • the conditions for isomerizing olefin metathesis include contacting a substance with one or more olefin isomerization catalysts.
  • one or more of the one or more olefin isomerization catalysts is capable of catalyzing olefin metathesis.
  • the conditions for isomerizing olefin metathesis include contacting a substance with one or more olefin metathesis catalysts and with one or more olefin isomerization catalysts.
  • the conditions for isomerizing olefin metathesis include conducting a batch reaction.
  • the conditions for isomerizing olefin metathesis include flowing one or more gases over the headspace of a batch reaction.
  • the conditions for isomerizing olefin metathesis include conducting a continuous-flow reaction.
  • the conditions for isomerizing olefin metathesis include flowing one or more gases selected from helium, argon, nitrogen, and hydrogen over the headspace of a batch reaction.
  • the conditions for isomerizing olefin metathesis include continuously removing one or more gases. In embodiments, the conditions for isomerizing olefin metathesis include continuously removing propene. In embodiments, the conditions for isomerizing olefin metathesis include continuously adding one or more gases. In embodiments, the conditions for isomerizing olefin metathesis include continuously adding ethylene. [0141] In embodiments, the method produces olefins. In embodiments, the method produces olefins that include fewer carbons per molecule than the substance. In embodiments, the method further includes reactive distillation. In embodiments, the method produces propene. In embodiments, the method produces propene in a yield of 0.1 to 100%.
  • the method produces propene in a yield of 50% to 100%. In embodiments, the method produces propene in a yield of 50% to 99.9%. In embodiments, the method produces propene in a yield of 50% to 99%. In embodiments, the method produces propene in a yield of 60% to 95%. In embodiments, the method produces propene in a selectivity of 0% to 100%. In embodiments, the method produces propene in a selectivity of 0.01% to 99.99%. In embodiments, the method produces propene in a selectivity of 1% to 99.99%. In embodiments, the method produces propene in a selectivity of 50% to 99.99%.
  • a method of making an alkene including mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (i) the dehydrogenated polymer includes at least 20 carbon atoms; or (ii) prior to the mixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer.
  • a method of making an alkene including mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (i) the dehydrogenated polymer includes at most 10% unsaturated alkene monomer units; (ii) the dehydrogenated polymer includes at least 20 carbon atoms; or (iii) prior to the mixing, the method includes mixing a polymer with one or more dehydrogenating reagent(s), thereby forming the dehydrogenated polymer.
  • a method of making a dehydrogenated polymer including mixing a polymer with one or more dehydrogenating reagent(s), wherein: (i) a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated; (ii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (iii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of 0.01% to 10% of monomer units are unsaturated; or (iv) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to from 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated;
  • the substituted or unsubstituted alkene is a substituted or unsubstituted propene.
  • the first substance is a substituted or unsubstituted dehydrogenated polyethylene.
  • the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da or from about 6,700 Da to about 15,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,000 Da.
  • the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 5,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 500,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 400,000 Da.
  • the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 300,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 200,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 100,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 80,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 60,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 40,000 Da.
  • the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 20,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from about 6,700 Da to about 15,000 Da. [0147] In embodiments, the the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 6,500 Da or from 6,700 Da to 15,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 6,500 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 6,000 Da.
  • the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 5,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 2,200 Da to 4,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 500,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 400,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 300,000 Da.
  • the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 200,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 100,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 80,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 60,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 40,000 Da. In embodiments, the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 20,000 Da.
  • the dehydrogenated polymer has a number average molecular weight of from 6,700 Da to 15,000 Da. [0148] In embodiments, a percentage of from about 10% or less of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 11% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 9% of monomer units in the dehydrogenated polymer are unsaturated.
  • a percentage of from about 0.01% to about 8% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 0.01% to about 1.5% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 2.4% to about 4.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 4.5% to about 13.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1% to about 3% of monomer units in the dehydrogenated polymer are unsaturated.
  • a percentage of from about 1.5% to about 3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from about 1.9% to about 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 1.7% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 1.8% of monomer units in the dehydrogenated polymer are unsaturated.
  • a percentage of about 1.9% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of about 2.3% of monomer units in the dehydrogenated polymer are unsaturated. [0149] In embodiments, a percentage of 10% or less of monomer units in the dehydrogenated polymer are unsaturated.
  • a percentage of from 0.01% to 11% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 9% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 8% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 0.01% to 1.5% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 2.4% to 4.3% of monomer units in the dehydrogenated polymer are unsaturated.
  • a percentage of from 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1% to 3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.5% to 3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.7% to 2.3% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.7% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of from 1.9% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated.
  • a percentage of 1.7% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 1.8% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 1.9% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2.1% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2.2% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, a percentage of 2.3% of monomer units in the dehydrogenated polymer are unsaturated.
  • the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.
  • the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 100,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.
  • the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 50,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 20,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.
  • the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 10,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated. In embodiments, the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.
  • the method further includes mixing the dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s), thereby forming an alkene.
  • the dehydrogenated polymer is a substituted or unsubstituted dehydrogenated polyethylene.
  • the alkene is a substituted or unsubstituted propene.
  • the dehydrogenated polymer, the one or more olefin metathesis reagent(s), and the one or more isomerization reagent(s) are mixed simultaneously.
  • the dehydrogenated polymer and the one or more olefin metathesis reagent(s) are mixed prior to adding the one or more isomerization reagent(s). In embodiments, the dehydrogenated polymer and one or more additional olefin metathesis reagent(s) are mixed prior to adding the one or more olefin metathesis reagent(s) and the one or more isomerization reagent(s). [0154] In embodiments, the one or more olefin metathesis reagent(s) includes an ethenolysis catalyst.
  • the one or more olefin metathesis reagent(s) includes one or more homogeneous olefin metathesis catalyst(s) or one or more heterogeneous olefin metathesis catalyst(s). In embodiments, the one or more olefin metathesis reagent(s) includes one or more homogeneous olefin metathesis catalyst(s). In embodiments, the one or more olefin metathesis reagent(s) includes one or more heterogeneous olefin metathesis catalyst(s). In embodiments, the one or more olefin metathesis reagent(s) further includes ethylene.
  • the homogeneous olefin metathesis catalyst is embodiments, the homogeneous olefin metathesis catalyst embodiments, the homogeneous olefin metathesis catalyst i embodiments, the homogeneous olefin metathesis catalyst homogeneous olefin metathesis catalyst .
  • the heterogeneous olefin metathesis catalyst is Re2O7/Al2O3 or WO3/Al2O3.
  • the heterogeneous olefin metathesis catalyst is Re2O7/Al2O3.
  • the heterogeneous olefin metathesis catalyst is WO 3 /Al 2 O 3 .
  • the one or more isomerization reagent(s) includes one or more homogeneous isomerization catalyst(s) or one or more heterogeneous isomerization catalyst(s). In embodiments, the one or more isomerization reagent(s) includes one or more homogeneous isomerization catalyst(s). In embodiments, the one or more isomerization reagent(s) includes one or more heterogeneous isomerization catalyst(s). [0158] In embodiments, the one or more homogeneous isomerization catalyst(s) is selected from: . In embodiments, the one or more homogeneous isomerization catalyst(s) is .
  • the one or omogeneous isomerization catalyst(s) is one or more homogeneous isomerization catalyst(s) is . embodiments, the one or more homogeneous isomerization catalyst(s) is . [0159] In embodiments, the one or more heterogeneous isomerization catalyst(s) is selected from: Na/Al2O3, K/Al2O3, Mg/Al2O3, MgO, NaO2, and KO2. In embodiments, the one or more heterogeneous isomerization catalyst(s) is Na/Al 2 O 3 . In embodiments, the one or more heterogeneous isomerization catalyst(s) is K/Al 2 O 3 .
  • the one or more heterogeneous isomerization catalyst(s) is Mg/Al2O3. In embodiments, the one or more heterogeneous isomerization catalyst(s) is MgO. In embodiments, the one or more heterogeneous isomerization catalyst(s) is NaO 2 . In embodiments, the one or more heterogeneous isomerization catalyst(s) is KO2. [0160] In embodiments, the one or more heterogeneous isomerization catalyst includes a Group VI or Group VII metal (W, Mo, Re) on SiO2 or Al2O3.
  • Group VI or Group VII metal (W, Mo, Re) on SiO 2 or Al 2 O 3 is first treated with a mild base (e.g., Na 2 CO 3 ). Without being bound to any particulary theory, in embodiments the mild base is sufficient to neutralize acidic sites.
  • the one or more heterogeneous isomerization catalyst includes K, Na, Na/K alloy, or Li supported on Al 2 O 3 .
  • the one or more heterogeneous isomerization catalyst includes includes an alkali metal (e.g., a Group VI or Group VII metal such as W, Mo, Re) and a SiO2 support.
  • the one or more heterogeneous isomerization catalyst includes K, Na, Na/K alloy, or Li supported on SiO2. [0161] In embodiments, the one or more heterogeneous metathesis catalyst further includes a tin promoter. In embodiments, the tin promotor is a tetraalkyl tin promotor. In embodiments, the one or more heterogeneous metathesis catalyst further includes a tetramethyl tin promoter. In embodiments, the one or more metathesis isomerization catalyst further includes a tetraethyl tin promoter. In embodiments, the one or more heterogeneous metathesis catalyst further includes a tetrapropyl tin promoter.
  • the one or more heterogeneous metathesis catalyst further includes a tetrabutyl tin promoter. In embodiments, the one or more heterogeneous metathesis catalyst further includes a tetrabenzyl tin promoter.
  • the substituted or unsubstituted polymer is a high-density polyethylene, a low-density polyethylene, or a linear low-density polyethylene, or a co-polymer thereof. In embodiments, the substituted or unsubstituted polymer is a high-density polyethylene. In embodiments, the substituted or unsubstituted polymer is a low-density polyethylene.
  • the substituted or unsubstituted polymer is a linear low-density polyethylene.
  • the one or more dehydrogenating reagent(s) includes a transfer dehydrogenation catalyst.
  • the one or more dehydrogenating reagent(s) includes a hydrogen acceptor.
  • the hydrogen acceptor includes a C-C bond.
  • the hydrogen acceptor includes a C ⁇ C bond.
  • the hydrogen acceptor includes an N-N bond.
  • the hydrogen acceptor is ethylene, propylene, butene, tert- butylethylene, norbornene, norbornadiene, butadiene, styrene, acetylene, O 2 , CO 2 , CO, substituted or unsubstituted benzoquinone, or N2.
  • the hydrogen acceptor is ethylene.
  • the hydrogen acceptor is propylene.
  • the hydrogen acceptor is butane.
  • the hydrogen acceptor is tert-butylethylene.
  • the hydrogen acceptor is norbornene.
  • the hydrogen acceptor is norbornadiene.
  • the hydrogen acceptor is butadiene. In embodiments, the hydrogen acceptor is styrene. In embodiments, the hydrogen acceptor is acetylene. In embodiments, the hydrogen acceptor is O 2 . In embodiments, the hydrogen acceptor is CO 2 . In embodiments, the hydrogen acceptor is CO. In embodiments, the hydrogen acceptor is substituted or unsubstituted benzoquinone. In embodiments, the hydrogen acceptor is N2. [0166] In embodiments, the one or more dehydrogenating reagent(s) includes a heterogeneous dehydrogenating catalyst. In embodiments, the heterogeneous dehydrogenating catalyst includes a plurality of metallic elements.
  • the heterogeneous dehydrogenating catalyst is a bimetallic catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is a Pt/Sn catalyst or a Pt/Zn catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is a Pt/Sn catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is a Pt/Zn catalyst. In embodiments, the heterogeneous dehydrogenating catalyst is Pt/Sn-Al 2 O 3 . In embodiments, the heterogeneous dehydrogenating catalyst is Pt/Zn-SiO 2 .
  • the one or more dehydrogenating reagent(s) includes a homogeneous dehydrogenating catalyst.
  • the homogeneous dehydrogenating catalyst includes an iridium catalyst.
  • the homogeneous dehydrogenating catalyst includes a rhodium catalyst.
  • the homogeneous dehydrogenating catalyst includes a ruthenium catalyst.
  • the one or more dehydrogenating reagent(s) includes (R)-( ⁇ )-5,5′- Bis[di(3,5-di-tert-butyl-4-methoxyphenyl)phosphino]-4,4′-bi-1,3-benzodioxole, [(4R)-(4,4′-bi- 1,3-benzodioxole)-5,5′-diyl]bis[bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphine], also commonly referred to as (R)-DTBM-SEGPHOS.
  • the one or more dehydrogenating reagent(s) includes (R)-( ⁇ )-5,5′-Bis[di(3,5-di-tert-butyl-4- methoxyphenyl)phosphino]-4,4′-bi-1,3-benzodioxole, [(4R)-(4,4′-bi-1,3-benzodioxole)-5,5′- diyl]bis[bis(3,5-di-tert-butyl-4-methoxyphenyl)phosphine] and an iridium catalyst.
  • the homogeneous dehydrogenating catalyst has the formula: .
  • M is Ir, Rh, Ru, or Os.
  • L 1 and L 2 are independently –O-, -S-, -NR 6 -, or substituted or unsubstituted alkylene (e.g., C1-C8, C1-C6, C1-C4, or C1-C2).
  • Each R 3 and R 4 is independently substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C 1 -C 4 , or C 1 -C 2 ), substituted or unsubstituted heteroalkyl (e.g., 2 to 8 membered, 2 to 6 membered, 4 to 6 membered, or 2 to 3 membered), substituted or unsubstituted cycloalkyl (e.g., C3-C8, C3-C6, C4-C6, or C5-C6), substituted or unsubstituted heterocycloalkyl (e.g., 3 to 8 membered, 3 to 6 membered, 4 to 6 membered, 4 to 5 membered, or 5 to 6 membered), substituted or unsubstituted aryl (e.g., C 6 -C 10 or phenyl), or substituted or unsubstituted heteroaryl (e.g., 5
  • R 5 is independently halogen, -CX 5 3, -CHX 5 2, -CH2X 5 , -OCX 5 3, -OCH2X 5 , -OCHX 5 2, -CN, -SOn5R 5D , -SOv5NR 5A R 5B , ⁇ NR 5C NR 5A R 5B , ⁇ ONR 5A R 5B , -NR 5C C(O)NR 5A R 5B , -N(O)m5, -NR 5A R 5B , -C(O)R 5C , -C(O)OR 5C , -OC(O)R 5C , -OC(O)OR 5C , -C(O)NR 5A R 5B , -OC(O)NR 5A R 5B , -OR 5D , -SR 5D , -NR 5A SO 2 R 5D , -NR 5A C(O)R 5C , -OR 5D
  • Each R 6 is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF 3 , -OCBr 3 , -OCI 3 , -OCHCl 2 , -OCHBr 2 , -OCHI 2 , -OCHF 2 , -OCH 2 Cl, -OCH 2 Br, -OCH 2 I, -OCH 2 F, substituted or unsubstituted alkyl (e.g., C 1 -C 8 , C 1 -C 6 , C 1 -C 4 , or C 1 -C 2 ), substituted or unsubstituted heteroalkyl (e.g.
  • Each R 5A , R 5B , R 5C , and R 5D is independently hydrogen, -CCl3, -CBr3, -CF3, -CI3, -CHCl2, -CHBr2, -CHF2, -CHI2, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CN, -OH, -NH2, -COOH, -CONH 2 , -OCCl 3 , -OCF 3 , -OCBr 3 , -OCI 3 , -OCHCl 2 , -OCHBr 2 , -OCHI 2 , -OCHF 2 , -OCH 2 Cl, -OCH2Br, -OCH2I, -OCH2F, substituted or unsubstituted alkyl (e.g., C1-C8, C1-C6, C1-C4, or C1- C2), substituted or unsubstituted alky
  • each X 5 is independently –Cl, -Br, -I, or –F.
  • the symbol n5 is 0, 1, 2, 3, or 4.
  • Each m5 and v5 is independently 1 or 2.
  • the symbol z5 is 0, 1, 2, or 3.
  • the homogeneous dehydrogenating catalyst has the formula: . M, L 1 , L 2 , R 3 , R 4 , and R 5 are as described herein, including in embodiments.
  • M is Ir, Rh, or Ru.
  • M is Ir.
  • M is Rh.
  • M is Ru.
  • M is Os.
  • a substituted L 1 (e.g., substituted alkylene) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted L 1 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • L 1 when L 1 is substituted, it is substituted with at least one substituent group.
  • when L 1 is substituted it is substituted with at least one size-limited substituent group.
  • when L 1 is substituted it is substituted with at least one lower substituent group.
  • L 1 is –O-, -S-, -NR 6 -, or unsubstituted C1-C10 alkylene. In embodiments, L 1 is –O-. In embodiments, L 1 is -S-. In embodiments, L 1 is -NR 6 -. In embodiments, L 1 is -NH-. In embodiments, L 1 is unsubstituted C 1 -C 10 alkylene. In embodiments, L 1 is unsubstituted methylene. In embodiments, L 1 is unsubstituted ethylene. In embodiments, L 1 is unsubstituted propylene. In embodiments, L 1 is unsubstituted n-propylene.
  • L 1 is unsubstituted isopropylene. In embodiments, L 1 is unsubstituted butylene. In embodiments, L 1 is unsubstituted n-butylene. In embodiments, L 1 is unsubstituted isobutylene. In embodiments, L 1 is unsubstituted tert-butylene. In embodiments, L 1 is substituted C 1 -C 10 alkylene. In embodiments, L 1 is substituted methylene. In embodiments, L 1 is substituted ethylene. In embodiments, L 1 is substituted propylene. In embodiments, L 1 is substituted n-propylene. In embodiments, L 1 is substituted isopropylene.
  • L 1 is substituted butylene. In embodiments, L 1 is substituted n-butylene. In embodiments, L 1 is substituted isobutylene. In embodiments, L 1 is substituted tert-butylene. In embodiments, the substituted alkylene is substituted with a substituent group.
  • a substituted L 2 (e.g., substituted alkylene) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted L 2 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • L 2 when L 2 is substituted, it is substituted with at least one substituent group.
  • when L 2 is substituted it is substituted with at least one size-limited substituent group.
  • when L 2 is substituted it is substituted with at least one lower substituent group.
  • L 2 is –O-, -S-, -NR 6 -, or unsubstituted C 1 -C 10 alkylene. In embodiments, L 2 is –O-. In embodiments, L 2 is -S-. In embodiments, L 2 is -NR 6 -. In embodiments, L 2 is -NH-. In embodiments, L 2 is unsubstituted C1-C10 alkylene. In embodiments, L 2 is unsubstituted methylene. In embodiments, L 2 is unsubstituted ethylene. In embodiments, L 2 is unsubstituted propylene. In embodiments, L 2 is unsubstituted n-propylene.
  • L 2 is unsubstituted isopropylene. In embodiments, L 2 is unsubstituted butylene. In embodiments, L 2 is unsubstituted n-butylene. In embodiments, L 2 is unsubstituted isobutylene. In embodiments, L 2 is unsubstituted tert-butylene. In embodiments, L 2 is substituted C1-C10 alkylene. In embodiments, L 2 is substituted methylene. In embodiments, L 2 is substituted ethylene. In embodiments, L 2 is substituted propylene. In embodiments, L 2 is substituted n-propylene. In embodiments, L 2 is substituted isopropylene.
  • L 2 is substituted butylene. In embodiments, L 2 is substituted n-butylene. In embodiments, L 2 is substituted isobutylene. In embodiments, L 2 is substituted tert-butylene. In embodiments, the substituted alkylene is substituted with a substituent group.
  • a substituted R 3 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 3 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 3 is substituted, it is substituted with at least one substituent group.
  • R 3 when R 3 is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 3 is substituted, it is substituted with at least one lower substituent group.
  • R 3 is unsubstituted C 1 -C 10 alkyl, unsubstituted 2 to 10 membered heteroalkyl, unsubstituted C3-C10 cycloalkyl, or unsubstituted phenyl. In embodiments, R 3 is unsubstituted C 1 -C 10 alkyl. In embodiments, R 3 is unsubstituted methyl. In embodiments, R 3 is unsubstituted ethyl.
  • R 3 is unsubstituted propyl. In embodiments, R 3 is unsubstituted n-propyl. In embodiments, R 3 is unsubstituted isopropyl. In embodiments, R 3 is unsubstituted butyl. In embodiments, R 3 is unsubstituted n-butyl. In embodiments, R 3 is unsubstituted isobutyl. In embodiments, R 3 is unsubstituted tert-butyl. In embodiments, R 3 is unsubstituted neopentyl. In embodiments, R 3 is unsubstituted 2 to 10 membered heteroalkyl.
  • R 3 is unsubstituted methoxy. In embodiments, R 3 is unsubstituted ethoxy. In embodiments, R 3 is unsubstituted propoxy. In embodiments, R 3 is independently n-propoxy. In embodiments, R 3 is unsubstituted isopropoxy. In embodiments, R 3 is unsubstituted butoxy. In embodiments, R 3 is unsubstituted n-butoxy. In embodiments, R 3 is unsubstituted isobutoxy. In embodiments, R 3 is unsubstituted tert-butoxy. In embodiments, R 3 is unsubstituted C 3 -C 10 cycloalkyl.
  • R 3 is unsubstituted adamantyl. In embodiments, R 3 is unsubstituted 1-adamantyl. In embodiments, R 3 is unsubstituted 2-adamantyl. In embodiments, R 3 is unsubstituted phenyl.
  • a substituted R 4 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 4 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 4 is substituted, it is substituted with at least one substituent group.
  • R 4 when R 4 is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 4 is substituted, it is substituted with at least one lower substituent group.
  • R 4 is unsubstituted C1-C10 alkyl, unsubstituted 2 to 10 membered heteroalkyl, unsubstituted C3-C10 cycloalkyl, or unsubstituted phenyl. In embodiments, R 4 is unsubstituted C 1 -C 10 alkyl. In embodiments, R 4 is unsubstituted methyl. In embodiments, R 4 is unsubstituted ethyl.
  • R 4 is unsubstituted propyl. In embodiments, R 4 is unsubstituted n-propyl. In embodiments, R 4 is unsubstituted isopropyl. In embodiments, R 4 is unsubstituted butyl. In embodiments, R 4 is unsubstituted n-butyl. In embodiments, R 4 is unsubstituted isobutyl. In embodiments, R 4 is unsubstituted tert-butyl. In embodiments, R 4 is unsubstituted neopentyl. In embodiments, R 4 is unsubstituted 2 to 10 membered heteroalkyl.
  • R 4 is unsubstituted methoxy. In embodiments, R 4 is unsubstituted ethoxy. In embodiments, R 4 is unsubstituted propoxy. In embodiments, R 4 is independently n-propoxy. In embodiments, R 4 is unsubstituted isopropoxy. In embodiments, R 4 is unsubstituted butoxy. In embodiments, R 4 is unsubstituted n-butoxy. In embodiments, R 4 is unsubstituted isobutoxy. In embodiments, R 4 is unsubstituted tert-butoxy. In embodiments, R 4 is unsubstituted C 3 -C 10 cycloalkyl.
  • R 4 is unsubstituted adamantyl. In embodiments, R 4 is unsubstituted 1-adamantyl. In embodiments, R 4 is unsubstituted 2-adamantyl. In embodiments, R 4 is unsubstituted phenyl.
  • a substituted R 5 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 5 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 5 is substituted, it is substituted with at least one substituent group.
  • R 5 when R 5 is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 5 is substituted, it is substituted with at least one lower substituent group.
  • R 5 is independently halogen, -CCl 3 , -CBr 3 , -CF 3 , -CI 3 , -CH 2 Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ⁇ NH2, ⁇ ONH2, ⁇ NHC(O)NHNH2, ⁇ NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -
  • R 5 is independently halogen. In embodiments, R 5 is independently –F. In embodiments, R 5 is independently –Cl. In embodiments, R 5 is independently –Br. In embodiments, R 5 is independently –I. In embodiments, R 5 is independently -CCl 3 . In embodiments, R 5 is independently -CBr3. In embodiments, R 5 is independently -CF3. In embodiments, R 5 is independently -CI3. In embodiments, R 5 is independently -CH2Cl. In embodiments, R 5 is independently -CH 2 Br. In embodiments, R 5 is independently -CH 2 F. In embodiments, R 5 is independently -CH2I. In embodiments, R 5 is independently -CHCl2.
  • R 5 is independently -CHBr2. In embodiments, R 5 is independently -CHF2. In embodiments, R 5 is independently -CHI 2 . In embodiments, R 5 is independently –CN. In embodiments, R 5 is independently –OR 5D . In embodiments, R 5 is independently –OCH 3 . In embodiments, R 5 is independently –OH. In embodiments, R 5 is independently -NH2. In embodiments, R 5 is independently –COOH. In embodiments, R 5 is independently -CONH2. In embodiments, R 5 is independently -NO2. In embodiments, R 5 is independently –SH. In embodiments, R 5 is independently -SO3H. In embodiments, R 5 is independently -OSO3H.
  • R 5 is independently -SO 2 NH 2 . In embodiments, R 5 is independently ⁇ NHNH 2 . In embodiments, R 5 is independently ⁇ ONH 2 . In embodiments, R 5 is independently ⁇ NHC(O)NHNH 2 . In embodiments, R 5 is independently ⁇ NHC(O)NH 2 . In embodiments, R 5 is independently -NHSO 2 H. In embodiments, R 5 is independently -NHC(O)H. In embodiments, R 5 is independently -NHC(O)OH. In embodiments, R 5 is independently –NHOH. In embodiments, R 5 is independently -OCCl3. In embodiments, R 5 is independently -OCBr3. In embodiments, R 5 is independently -OCF3.
  • R 5 is independently -OCI3. In embodiments, R 5 is independently -OCH 2 Cl. In embodiments, R 5 is independently -OCH 2 Br. In embodiments, R 5 is independently -OCH2F. In embodiments, R 5 is independently -OCH2I. In embodiments, R 5 is independently -OCHCl2. In embodiments, R 5 is independently -OCHBr2. In embodiments, R 5 is independently -OCHF 2 . In embodiments, R 5 is independently -OCHI 2 . In embodiments, R 5 is independently -OP(R 5A )(R 5B ). In embodiments, R 5 is independently -OP(C(CH3)3)2.
  • R 5 is independently unsubstituted C1-C10 alkyl. In embodiments, R 5 is independently unsubstituted methyl. In embodiments, R 5 is independently unsubstituted ethyl. In embodiments, R 5 is independently unsubstituted propyl. In embodiments, R 5 is independently unsubstituted n-propyl. In embodiments, R 5 is independently unsubstituted isopropyl. In embodiments, R 5 is independently unsubstituted butyl. In embodiments, R 5 is independently unsubstituted n-butyl. In embodiments, R 5 is independently unsubstituted isobutyl.
  • R 5 is independently unsubstituted tert-butyl. In embodiments, R 5 is independently unsubstituted 2 to 4 membered heteroalkyl. In embodiments, R 5 is independently unsubstituted methoxy. In embodiments, R 5 is independently unsubstituted ethoxy. In embodiments, R 5 is independently unsubstituted propoxy. In embodiments, R 5 is independently unsubstituted n-propoxy. In embodiments, R 5 is independently unsubstituted isopropoxy. In embodiments, R 5 is independently unsubstituted butoxy. In embodiments, R 5 is independently unsubstituted n-butoxy.
  • R 5 is independently unsubstituted isobutoxy. In embodiments, R 5 is independently unsubstituted tert-butoxy.
  • a substituted R 5A e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, unsubstitut aerdyl, and/or substituted heteroaryl
  • R 5A is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 5A is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • R 5A when R 5A is substituted, it is substituted with at least one substituent group. In embodiments, when R 5A is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 5A is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 5B (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 5B is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 5B is substituted, it is substituted with at least one substituent group.
  • R 5B when R 5B is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 5B is substituted, it is substituted with at least one lower substituent group.
  • a substituted ring formed when R 5A and R 5B substituents bonded to the same nitrogen atom are joined e.g., substituted heterocycloalkyl and/or substituted heteroaryl
  • R 5A and R 5B substituents bonded to the same nitrogen atom are joined is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted ring formed when R 5A and R 5B substituents bonded to the same nitrogen atom are joined is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • when the substituted ring formed when R 5A and R 5B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one substituent group. In embodiments, when the substituted ring formed when R 5A and R 5B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when the substituted ring formed when R 5A and R 5B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 5C (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 5C is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 5C is substituted, it is substituted with at least one substituent group.
  • R 5C when R 5C is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 5C is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 5D e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl
  • R 5D is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 5D is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • R 5D when R 5D is substituted, it is substituted with at least one substituent group. In embodiments, when R 5D is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 5D is substituted, it is substituted with at least one lower substituent group.
  • R 5A is independently hydrogen or unsubstituted C 1 -C 4 alkyl. In embodiments, R 5A is independently hydrogen. In embodiments, R 5A is independently unsubstituted C1-C4 alkyl. In embodiments, R 5A is independently unsubstituted methyl. In embodiments, R 5A is independently unsubstituted ethyl.
  • R 5A is independently unsubstituted propyl. In embodiments, R 5A is independently unsubstituted n-propyl. In embodiments, R 5A is independently unsubstituted isopropyl. In embodiments, R 5A is independently unsubstituted butyl. In embodiments, R 5A is independently unsubstituted n-butyl. In embodiments, R 5A is independently unsubstituted isobutyl. In embodiments, R 5A is independently unsubstituted tert-butyl. [0199] In embodiments, R 5B is independently hydrogen or unsubstituted C 1 -C 4 alkyl. In embodiments, R 5B is independently hydrogen.
  • R 5B is independently unsubstituted C1-C4 alkyl. In embodiments, R 5B is independently unsubstituted methyl. In embodiments, R 5B is independently unsubstituted ethyl. In embodiments, R 5B is independently unsubstituted propyl. In embodiments, R 5B is independently unsubstituted n-propyl. In embodiments, R 5B is independently unsubstituted isopropyl. In embodiments, R 5B is independently unsubstituted butyl. In embodiments, R 5B is independently unsubstituted n-butyl. In embodiments, R 5B is independently unsubstituted isobutyl.
  • R 5B is independently unsubstituted tert-butyl.
  • R 5C is independently hydrogen or unsubstituted C1-C4 alkyl. In embodiments, R 5C is independently hydrogen. In embodiments, R 5C is independently unsubstituted C 1 -C 4 alkyl. In embodiments, R 5C is independently unsubstituted methyl. In embodiments, R 5C is independently unsubstituted ethyl. In embodiments, R 5C is independently unsubstituted propyl. In embodiments, R 5C is independently unsubstituted n-propyl. In embodiments, R 5C is independently unsubstituted isopropyl.
  • R 5C is independently unsubstituted butyl. In embodiments, R 5C is independently unsubstituted n-butyl. In embodiments, R 5C is independently unsubstituted isobutyl. In embodiments, R 5C is independently unsubstituted tert-butyl. [0201] In embodiments, R 5D is independently hydrogen or unsubstituted C1-C4 alkyl. In embodiments, R 5D is independently hydrogen. In embodiments, R 5D is independently unsubstituted C 1 -C 4 alkyl. In embodiments, R 5D is independently unsubstituted methyl. In embodiments, R 5D is independently unsubstituted ethyl.
  • R 5D is independently unsubstituted propyl. In embodiments, R 5D is independently unsubstituted n-propyl. In embodiments, R 5D is independently unsubstituted isopropyl. In embodiments, R 5D is independently unsubstituted butyl. In embodiments, R 5D is independently unsubstituted n-butyl. In embodiments, R 5D is independently unsubstituted isobutyl. In embodiments, R 5D is independently unsubstituted tert-butyl. [0202] In embodiments, z5 is 0. In embodiments, z5 is 1. In embodiments, z5 is 2. In embodiments, z5 is 3.
  • a substituted R 6 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 6 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 6 is substituted, it is substituted with at least one substituent group.
  • R 6 when R 6 is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 6 is substituted, it is substituted with at least one lower substituent group.
  • R 6 is independently hydrogen or unsubstituted C 1 -C 4 alkyl. In embodiments, R 6 is independently hydrogen. In embodiments, R 6 is independently unsubstituted C1-C4 alkyl. In embodiments, R 6 is independently unsubstituted methyl. In embodiments, R 6 is independently unsubstituted ethyl. In embodiments, R 6 is independently unsubstituted propyl. In embodiments, R 6 is independently unsubstituted n-propyl.
  • R 1 is independently hydrogen, halogen, -CX 1 3, -CHX 1 2, -CH2X 1 , -OCX 1 3, -OCH2X 1 , -OCHX 1 2, -CN, -SOn1R 1D , -SOv1NR 1A R 1B , ⁇ NR 1C NR 1A R 1B , ⁇ ONR 1A R 1B , -NR 1C C(O)NR 1A R 1B , -N(O)m1, -NR 1A R 1B , -C(O)R 1C , -C(O)OR 1C , -OC(O)R 1C , -OC(O)OR 1C , -C(O)NR 1A R 1B , -OC(O)NR 1A R 1B , -OR 1D , -SR 1D , -NR 1A SO 2 R 1D , -NR 1A C(O)R 1C ,
  • R 2 is independently hydrogen, halogen, -CX 2 3, -CHX 2 2, -CH2X 2 , -OCX 2 3, -OCH 2 X 2 , -OCHX 2 2 , -CN, -SO n2 R 2D , -SO v2 NR 2A R 2B , ⁇ NR 2C NR 2A R 2B , ⁇ ONR 2A R 2B , -NR 2C C(O)NR 2A R 2B , -N(O) m2 , -NR 2A R 2B , -C(O)R 2C , -C(O)OR 2C , -OC(O)R 2C , -OC(O)OR 2C , -C(O)NR 2A R 2B , -OC(O)NR 2A R 2B , -OR 2D , -SR 2D , -NR 2A SO 2 R 2D , -NR 2A
  • Each R 1A , R 1B , R 1C , R 1D , R 2A , R 2B , R 2C , and R 2D is independently hydrogen, -CCl 3 , -CBr 3 , -CF 3 , -CI 3 , -CHCl 2 , -CHBr 2 , -CHF 2 , -CHI 2 , -CH 2 Cl, -CH 2 Br, -CH 2 F, -CH 2 I, -CN, -OH, -NH2, -COOH, -CONH2, -OCCl3, -OCF3, -OCBr3, -OCI3, -OCHCl2, -OCHBr2, -OCHI2, -OCHF 2 , -OCH 2 Cl, -OCH 2 Br, -OCH 2 I, -OCH 2 F, substituted or unsubstituted alkyl (e.g., C 1 -C 8 , C 1 -C
  • Each X 1 and X 2 is independently –Cl, -Br, -I, or –F.
  • Each n1 and n2 is independently 0, 1, 2, 3, or 4.
  • Each m1, m2, v1, and v2 is independently 1 or 2.
  • a substituted R 1 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 1 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 1 is substituted, it is substituted with at least one substituent group.
  • R 1 when R 1 is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 1 is substituted, it is substituted with at least one lower substituent group.
  • R 1 is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH 2 Cl, -CH 2 Br, -CH 2 F, -CH 2 I, -CHCl 2 , -CHBr 2 , -CHF 2 , -CHI 2 , -CN, -OH, -NH 2 , -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -
  • R 1 is independently hydrogen, halogen, -CCl 3 , -CBr 3 , -CF 3 , -CI 3 , -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ⁇ NHNH2, ⁇ ONH2, ⁇ NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH 2 F, -OCH 2 I, -OCHCl 2 , -OCHBr
  • R 1 is independently hydrogen. In embodiments, R 1 is independently substituted or unsubstituted C 1 -C 1000 alkyl. In embodiments, R 1 is independently substituted or unsubstituted C1-C500 alkyl. In embodiments, R 1 is independently substituted or unsubstituted C1-C100 alkyl. In embodiments, R 1 is independently substituted or unsubstituted C1-C50 alkyl. In embodiments, R 1 is independently substituted or unsubstituted C 1 -C 20 alkyl. In embodiments, R 1 is independently substituted or unsubstituted C 1 -C 10 alkyl.
  • R 1 is independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R 1 is independently unsubstituted methyl. In embodiments, R 1 is independently unsubstituted ethyl. In embodiments, R 1 is independently unsubstituted propyl. In embodiments, R 1 is independently unsubstituted n- propyl. In embodiments, R 1 is independently unsubstituted isopropyl. In embodiments, R 1 is independently unsubstituted butyl. In embodiments, R 1 is independently unsubstituted n-butyl. In embodiments, R 1 is independently unsubstituted tert-butyl.
  • a substituted R 1A (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 1A is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 1A is substituted, it is substituted with at least one substituent group.
  • R 1A when R 1A is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 1A is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 1B e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl
  • R 1B is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 1B is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • a substituted ring formed when R 1A and R 1B substituents bonded to the same nitrogen atom are joined e.g., substituted heterocycloalkyl and/or substituted heteroaryl
  • at least one substituent group, size-limited substituent group, or lower substituent group e.g., substituted heterocycloalkyl and/or substituted heteroaryl
  • the substituted ring formed when R 1A and R 1B substituents bonded to the same nitrogen atom are joined is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • when the substituted ring formed when R 1A and R 1B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one substituent group. In embodiments, when the substituted ring formed when R 1A and R 1B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when the substituted ring formed when R 1A and R 1B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 1C (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 1C is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 1C is substituted, it is substituted with at least one substituent group.
  • R 1C when R 1C is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 1C is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 1D e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl
  • R 1D is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 1D is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • R 1D when R 1D is substituted, it is substituted with at least one substituent group. In embodiments, when R 1D is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 1D is substituted, it is substituted with at least one lower substituent group.
  • R 1A is independently hydrogen. In embodiments, R 1A is independently substituted or unsubstituted C 1 -C 5 alkyl. In embodiments, R 1A is independently unsubstituted methyl. In embodiments, R 1A is independently unsubstituted ethyl. In embodiments, R 1A is independently unsubstituted propyl.
  • R 1A is independently unsubstituted n-propyl. In embodiments, R 1A is independently unsubstituted isopropyl. In embodiments, R 1A is independently unsubstituted butyl. In embodiments, R 1A is independently unsubstituted n-butyl. In embodiments, R 1A is independently unsubstituted tert-butyl. [0223] In embodiments, R 1B is independently hydrogen. In embodiments, R 1B is independently substituted or unsubstituted C 1 -C 5 alkyl. In embodiments, R 1B is independently unsubstituted methyl. In embodiments, R 1B is independently unsubstituted ethyl.
  • R 1B is independently unsubstituted propyl. In embodiments, R 1B is independently unsubstituted n-propyl. In embodiments, R 1B is independently unsubstituted isopropyl. In embodiments, R 1B is independently unsubstituted butyl. In embodiments, R 1B is independently unsubstituted n-butyl. In embodiments, R 1B is independently unsubstituted tert-butyl. [0224] In embodiments, R 1C is independently hydrogen. In embodiments, R 1C is independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R 1C is independently unsubstituted methyl.
  • R 1C is independently unsubstituted ethyl. In embodiments, R 1C is independently unsubstituted propyl. In embodiments, R 1C is independently unsubstituted n-propyl. In embodiments, R 1C is independently unsubstituted isopropyl. In embodiments, R 1C is independently unsubstituted butyl. In embodiments, R 1C is independently unsubstituted n-butyl. In embodiments, R 1C is independently unsubstituted tert-butyl. [0225] In embodiments, R 1D is independently hydrogen. In embodiments, R 1D is independently substituted or unsubstituted C1-C5 alkyl.
  • R 1D is independently unsubstituted methyl. In embodiments, R 1D is independently unsubstituted ethyl. In embodiments, R 1D is independently unsubstituted propyl. In embodiments, R 1D is independently unsubstituted n-propyl. In embodiments, R 1D is independently unsubstituted isopropyl. In embodiments, R 1D is independently unsubstituted butyl. In embodiments, R 1D is independently unsubstituted n-butyl. In embodiments, R 1D is independently unsubstituted tert-butyl.
  • a substituted R 2 (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 2 is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 2 is substituted, it is substituted with at least one substituent group.
  • R 2 when R 2 is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 2 is substituted, it is substituted with at least one lower substituent group.
  • R 2 is independently hydrogen, halogen, -CCl 3 , -CBr 3 , -CF 3 , -CI 3 , -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -NHOH, -
  • R 2 is independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI2, -CN, -OH, -NH2, -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl 3 , -OCBr 3 , -OCF 3 , -OCI 3 , -OCH 2 Cl, -OCH 2 Br, -OCH2F, -OCH2I, --
  • R 2 is independently hydrogen. In embodiments, R 2 is independently substituted or unsubstituted C1-C1000 alkyl. In embodiments, R 2 is independently substituted or unsubstituted C1-C500 alkyl. In embodiments, R 2 is independently substituted or unsubstituted C 1 -C 100 alkyl. In embodiments, R 2 is independently substituted or unsubstituted C 1 -C 50 alkyl. In embodiments, R 2 is independently substituted or unsubstituted C 1 -C 20 alkyl. In embodiments, R 2 is independently substituted or unsubstituted C1-C10 alkyl.
  • R 2 is independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R 2 is independently unsubstituted methyl. In embodiments, R 2 is independently unsubstituted ethyl. In embodiments, R 2 is independently unsubstituted propyl. In embodiments, R 2 is independently unsubstituted n- propyl. In embodiments, R 2 is independently unsubstituted isopropyl. In embodiments, R 2 is independently unsubstituted butyl. In embodiments, R 2 is independently unsubstituted n-butyl. In embodiments, R 2 is independently unsubstituted tert-butyl.
  • a substituted R 2A (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 2A is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 2A is substituted, it is substituted with at least one substituent group.
  • R 2A when R 2A is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 2A is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 2B e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl
  • R 2B is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 2B is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • R 2B when R 2B is substituted, it is substituted with at least one substituent group. In embodiments, when R 2B is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 2B is substituted, it is substituted with at least one lower substituent group.
  • a substituted ring formed when R 2A and R 2B substituents bonded to the same nitrogen atom are joined e.g., substituted heterocycloalkyl and/or substituted heteroaryl
  • at least one substituent group, size-limited substituent group, or lower substituent group e.g., substituted heterocycloalkyl and/or substituted heteroaryl
  • the substituted ring formed when R 2A and R 2B substituents bonded to the same nitrogen atom are joined is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • when the substituted ring formed when R 2A and R 2B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one substituent group. In embodiments, when the substituted ring formed when R 2A and R 2B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when the substituted ring formed when R 2A and R 2B substituents bonded to the same nitrogen atom are joined is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 2C (e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl) is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 2C is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different. In embodiments, when R 2C is substituted, it is substituted with at least one substituent group.
  • R 2C when R 2C is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 2C is substituted, it is substituted with at least one lower substituent group.
  • a substituted R 2D e.g., substituted alkyl, substituted heteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl, and/or substituted heteroaryl
  • R 2D is substituted with at least one substituent group, size-limited substituent group, or lower substituent group; wherein if the substituted R 2D is substituted with a plurality of groups selected from substituent groups, size-limited substituent groups, and lower substituent groups; each substituent group, size-limited substituent group, and/or lower substituent group may optionally be different.
  • R 2D when R 2D is substituted, it is substituted with at least one substituent group. In embodiments, when R 2D is substituted, it is substituted with at least one size-limited substituent group. In embodiments, when R 2D is substituted, it is substituted with at least one lower substituent group.
  • R 2A is independently hydrogen. In embodiments, R 2A is independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R 2A is independently unsubstituted methyl. In embodiments, R 2A is independently unsubstituted ethyl. In embodiments, R 2A is independently unsubstituted propyl.
  • R 2A is independently unsubstituted n-propyl. In embodiments, R 2A is independently unsubstituted isopropyl. In embodiments, R 2A is independently unsubstituted butyl. In embodiments, R 2A is independently unsubstituted n-butyl. In embodiments, R 2A is independently unsubstituted tert-butyl. [0236] In embodiments, R 2B is independently hydrogen. In embodiments, R 2B is independently substituted or unsubstituted C1-C5 alkyl. In embodiments, R 2B is independently unsubstituted methyl. In embodiments, R 2B is independently unsubstituted ethyl.
  • R 2B is independently unsubstituted propyl. In embodiments, R 2B is independently unsubstituted n-propyl. In embodiments, R 2B is independently unsubstituted isopropyl. In embodiments, R 2B is independently unsubstituted butyl. In embodiments, R 2B is independently unsubstituted n-butyl. In embodiments, R 2B is independently unsubstituted tert-butyl. [0237] In embodiments, R 2C is independently hydrogen. In embodiments, R 2C is independently substituted or unsubstituted C 1 -C 5 alkyl. In embodiments, R 2C is independently unsubstituted methyl.
  • R 2C is independently unsubstituted ethyl. In embodiments, R 2C is independently unsubstituted propyl. In embodiments, R 2C is independently unsubstituted n-propyl. In embodiments, R 2C is independently unsubstituted isopropyl. In embodiments, R 2C is independently unsubstituted butyl. In embodiments, R 2C is independently unsubstituted n-butyl. In embodiments, R 2C is independently unsubstituted tert-butyl. [0238] In embodiments, R 2D is independently hydrogen. In embodiments, R 2D is independently substituted or unsubstituted C 1 -C 5 alkyl.
  • R 2D is independently unsubstituted methyl. In embodiments, R 2D is independently unsubstituted ethyl. In embodiments, R 2D is independently unsubstituted propyl. In embodiments, R 2D is independently unsubstituted n-propyl. In embodiments, R 2D is independently unsubstituted isopropyl. In embodiments, R 2D is independently unsubstituted butyl. In embodiments, R 2D is independently unsubstituted n-butyl. In embodiments, R 2D is independently unsubstituted tert-butyl. [0239] In embodiments, the method is conducted under continuous flow conditions.
  • R 1 when R 1 is substituted, R 1 is substituted with one or more first substituent groups denoted by R 1.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1.1 substituent group when an R 1.1 substituent group is substituted, the R 1.1 substituent group is substituted with one or more second substituent groups denoted by R 1.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1.2 substituent group when an R 1.2 substituent group is substituted, the R 1.2 substituent group is substituted with one or more third substituent groups denoted by R 1.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1 , R 1.1 , R 1.2 , and R 1.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 1 , R 1.1 , R 1.2 , and R 1.3 , respectively.
  • R 1A when R 1A is substituted, R 1A is substituted with one or more first substituent groups denoted by R 1A.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1A.1 substituent group when an R 1A.1 substituent group is substituted, the R 1A.1 substituent group is substituted with one or more second substituent groups denoted by R 1A.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1A.2 substituent group when an R 1A.2 substituent group is substituted, the R 1A.2 substituent group is substituted with one or more third substituent groups denoted by R 1A.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1A , R 1A.1 , R 1A.2 , and R 1A.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 1A , R 1A.1 , R 1A.2 , and R 1A.3 , respectively.
  • R 1B when R 1B is substituted, R 1B is substituted with one or more first substituent groups denoted by R 1B.1 as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R 1B.1 substituent group is substituted, the R 1B.1 substituent group is substituted with one or more second substituent groups denoted by R 1B.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1B.2 substituent group when an R 1B.2 substituent group is substituted, the R 1B.2 substituent group is substituted with one or more third substituent groups denoted by R 1B.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1B , R 1B.1 , R 1B.2 , and R 1B.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 1B , R 1B.1 , R 1B.2 , and R 1B.3 , respectively.
  • R 1A and R 1B substituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R 1A.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1A.1 when an R 1A.1 substituent group is substituted, the R 1A.1 substituent group is substituted with one or more second substituent groups denoted by R 1A.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1A.2 substituent group when an R 1A.2 substituent group is substituted, the R 1A.2 substituent group is substituted with one or more third substituent groups denoted by R 1A.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1A.1 , R 1A.2 , and R 1A.3 have values corresponding to the values of R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW.1 , R WW.2 , and R WW.3 correspond to R 1A.1 , R 1A.2 , and R 1A.3 , respectively.
  • R 1A and R 1B substituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R 1B.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1B.1 when an R 1B.1 substituent group is substituted, the R 1B.1 substituent group is substituted with one or more second substituent groups denoted by R 1B.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1B.2 substituent group when an R 1B.2 substituent group is substituted, the R 1B.2 substituent group is substituted with one or more third substituent groups denoted by R 1B.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1B.1 , R 1B.2 , and R 1B.3 have values corresponding to the values of R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW.1 , R WW.2 , and R WW.3 correspond to R 1B.1 , R 1B.2 , and R 1B.3 , respectively.
  • R 1C when R 1C is substituted, R 1C is substituted with one or more first substituent groups denoted by R 1C.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1C.1 when an R 1C.1 substituent group is substituted, the R 1C.1 substituent group is substituted with one or more second substituent groups denoted by R 1C.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1C.2 substituent group when an R 1C.2 substituent group is substituted, the R 1C.2 substituent group is substituted with one or more third substituent groups denoted by R 1C.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1C , R 1C.1 , R 1C.2 , and R 1C.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 1C , R 1C.1 , R 1C.2 , and R 1C.3 , respectively.
  • R 1D when R 1D is substituted, R 1D is substituted with one or more first substituent groups denoted by R 1D.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1D.1 when an R 1D.1 substituent group is substituted, the R 1D.1 substituent group is substituted with one or more second substituent groups denoted by R 1D.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 1D , R 1D.1 , R 1D.2 , and R 1D.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 1D , R 1D.1 , R 1D.2 , and R 1D.3 , respectively.
  • R 2 when R 2 is substituted, R 2 is substituted with one or more first substituent groups denoted by R 2.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2.1 substituent group when an R 2.1 substituent group is substituted, the R 2.1 substituent group is substituted with one or more second substituent groups denoted by R 2.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2.2 substituent group when an R 2.2 substituent group is substituted, the R 2.2 substituent group is substituted with one or more third substituent groups denoted by R 2.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2 , R 2.1 , R 2.2 , and R 2.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 2 , R 2.1 , R 2.2 , and R 2.3 , respectively.
  • R 2A when R 2A is substituted, R 2A is substituted with one or more first substituent groups denoted by R 2A.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2A.1 substituent group when an R 2A.1 substituent group is substituted, the R 2A.1 substituent group is substituted with one or more second substituent groups denoted by R 2A.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2A.2 substituent group when an R 2A.2 substituent group is substituted, the R 2A.2 substituent group is substituted with one or more third substituent groups denoted by R 2A.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2A , R 2A.1 , R 2A.2 , and R 2A.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 2A , R 2A.1 , R 2A.2 , and R 2A.3 , respectively.
  • R 2B when R 2B is substituted, R 2B is substituted with one or more first substituent groups denoted by R 2B.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2B.1 substituent group when an R 2B.1 substituent group is substituted, the R 2B.1 substituent group is substituted with one or more second substituent groups denoted by R 2B.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2B.2 substituent group when an R 2B.2 substituent group is substituted, the R 2B.2 substituent group is substituted with one or more third substituent groups denoted by R 2B.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2B , R 2B.1 , R 2B.2 , and R 2B.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 2B , R 2B.1 , R 2B.2 , and R 2B.3 , respectively.
  • R 2A and R 2B substituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R 2A.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2A.1 substituent group when an R 2A.1 substituent group is substituted, the R 2A.1 substituent group is substituted with one or more second substituent groups denoted by R 2A.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2A.2 substituent group when an R 2A.2 substituent group is substituted, the R 2A.2 substituent group is substituted with one or more third substituent groups denoted by R 2A.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2A.1 , R 2A.2 , and R 2A.3 have values corresponding to the values of R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW.1 , R WW.2 , and R WW.3 correspond to R 2A.1 , R 2A.2 , and R 2A.3 , respectively.
  • R 2A and R 2B substituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R 2B.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2B.1 substituent group when an R 2B.1 substituent group is substituted, the R 2B.1 substituent group is substituted with one or more second substituent groups denoted by R 2B.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2B.2 substituent group when an R 2B.2 substituent group is substituted, the R 2B.2 substituent group is substituted with one or more third substituent groups denoted by R 2B.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2B.1 , R 2B.2 , and R 2B.3 have values corresponding to the values of R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW.1 , R WW.2 , and R WW.3 correspond to R 2B.1 , R 2B.2 , and R 2B.3 , respectively.
  • R 2C when R 2C is substituted, R 2C is substituted with one or more first substituent groups denoted by R 2C.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2C.1 substituent group when an R 2C.1 substituent group is substituted, the R 2C.1 substituent group is substituted with one or more second substituent groups denoted by R 2C.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2C.2 substituent group when an R 2C.2 substituent group is substituted, the R 2C.2 substituent group is substituted with one or more third substituent groups denoted by R 2C.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2C , R 2C.1 , R 2C.2 , and R 2C.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 2C , R 2C.1 , R 2C.2 , and R 2C.3 , respectively.
  • R 2D when R 2D is substituted, R 2D is substituted with one or more first substituent groups denoted by R 2D.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2D.1 substituent group when an R 2D.1 substituent group is substituted, the R 2D.1 substituent group is substituted with one or more second substituent groups denoted by R 2D.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2D.2 substituent group when an R 2D.2 substituent group is substituted, the R 2D.2 substituent group is substituted with one or more third substituent groups denoted by R 2D.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 2D , R 2D.1 , R 2D.2 , and R 2D.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 2D , R 2D.1 , R 2D.2 , and R 2D.3 , respectively.
  • R 3 when R 3 is substituted, R 3 is substituted with one or more first substituent groups denoted by R 3.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 3.1 substituent group when an R 3.1 substituent group is substituted, the R 3.1 substituent group is substituted with one or more second substituent groups denoted by R 3.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 3.2 substituent group when an R 3.2 substituent group is substituted, the R 3.2 substituent group is substituted with one or more third substituent groups denoted by R 3.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 3 , R 3.1 , R 3.2 , and R 3.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 3 , R 3.1 , R 3.2 , and R 3.3 , respectively.
  • R 4 when R 4 is substituted, R 4 is substituted with one or more first substituent groups denoted by R 4.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 4.1 substituent group when an R 4.1 substituent group is substituted, the R 4.1 substituent group is substituted with one or more second substituent groups denoted by R 4.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 4.2 substituent group when an R 4.2 substituent group is substituted, the R 4.2 substituent group is substituted with one or more third substituent groups denoted by R 4.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 4 , R 4.1 , R 4.2 , and R 4.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 4 , R 4.1 , R 4.2 , and R 4.3 , respectively.
  • R 5 when R 5 is substituted, R 5 is substituted with one or more first substituent groups denoted by R 5.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5.1 substituent group when an R 5.1 substituent group is substituted, the R 5.1 substituent group is substituted with one or more second substituent groups denoted by R 5.2 as explained in the definitions section above in the description of “first substituent group(s)”. In embodiments, when an R 5.2 substituent group is substituted, the R 5.2 substituent group is substituted with one or more third substituent groups denoted by R 5.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5 , R 5.1 , R 5.2 , and R 5.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 5 , R 5.1 , R 5.2 , and R 5.3 , respectively.
  • R 5A when R 5A is substituted, R 5A is substituted with one or more first substituent groups denoted by R 5A.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5A.1 substituent group when an R 5A.1 substituent group is substituted, the R 5A.1 substituent group is substituted with one or more second substituent groups denoted by R 5A.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5A.2 substituent group when an R 5A.2 substituent group is substituted, the R 5A.2 substituent group is substituted with one or more third substituent groups denoted by R 5A.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5A , R 5A.1 , R 5A.2 , and R 5A.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 5A , R 5A.1 , R 5A.2 , and R 5A.3 , respectively.
  • R 5B when R 5B is substituted, R 5B is substituted with one or more first substituent groups denoted by R 5B.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5B.1 substituent group when an R 5B.1 substituent group is substituted, the R 5B.1 substituent group is substituted with one or more second substituent groups denoted by R 5B.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5B.2 substituent group when an R 5B.2 substituent group is substituted, the R 5B.2 substituent group is substituted with one or more third substituent groups denoted by R 5B.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5B , R 5B.1 , R 5B.2 , and R 5B.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 5B , R 5B.1 , R 5B.2 , and R 5B.3 , respectively.
  • R 5A and R 5B substituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R 5A.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5A.1 when an R 5A.1 substituent group is substituted, the R 5A.1 substituent group is substituted with one or more second substituent groups denoted by R 5A.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5A.2 substituent group when an R 5A.2 substituent group is substituted, the R 5A.2 substituent group is substituted with one or more third substituent groups denoted by R 5A.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5A.1 , R 5A.2 , and R 5A.3 have values corresponding to the values of R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW.1 , R WW.2 , and R WW.3 correspond to R 5A.1 , R 5A.2 , and R 5A.3 , respectively.
  • R 5A and R 5B substituents bonded to the same nitrogen atom are optionally joined to form a moiety that is substituted (e.g., a substituted heterocycloalkyl or substituted heteroaryl), the moiety is substituted with one or more first substituent groups denoted by R 5B.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5B.1 when an R 5B.1 substituent group is substituted, the R 5B.1 substituent group is substituted with one or more second substituent groups denoted by R 5B.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5B.2 substituent group when an R 5B.2 substituent group is substituted, the R 5B.2 substituent group is substituted with one or more third substituent groups denoted by R 5B.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5B.1 , R 5B.2 , and R 5B.3 have values corresponding to the values of R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW.1 , R WW.2 , and R WW.3 correspond to R 5B.1 , R 5B.2 , and R 5B.3 , respectively.
  • R 5C when R 5C is substituted, R 5C is substituted with one or more first substituent groups denoted by R 5C.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5C.1 when an R 5C.1 substituent group is substituted, the R 5C.1 substituent group is substituted with one or more second substituent groups denoted by R 5C.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5C.2 substituent group when an R 5C.2 substituent group is substituted, the R 5C.2 substituent group is substituted with one or more third substituent groups denoted by R 5C.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5C , R 5C.1 , R 5C.2 , and R 5C.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 5C , R 5C.1 , R 5C.2 , and R 5C.3 , respectively.
  • R 5D when R 5D is substituted, R 5D is substituted with one or more first substituent groups denoted by R 5D.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5D.1 when an R 5D.1 substituent group is substituted, the R 5D.1 substituent group is substituted with one or more second substituent groups denoted by R 5D.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5D.2 substituent group when an R 5D.2 substituent group is substituted, the R 5D.2 substituent group is substituted with one or more third substituent groups denoted by R 5D.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 5D , R 5D.1 , R 5D.2 , and R 5D.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 5D , R 5D.1 , R 5D.2 , and R 5D.3 , respectively.
  • R 6 when R 6 is substituted, R 6 is substituted with one or more first substituent groups denoted by R 6.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 6.1 substituent group when an R 6.1 substituent group is substituted, the R 6.1 substituent group is substituted with one or more second substituent groups denoted by R 6.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 6.2 substituent group when an R 6.2 substituent group is substituted, the R 6.2 substituent group is substituted with one or more third substituent groups denoted by R 6.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R 6 , R 6.1 , R 6.2 , and R 6.3 have values corresponding to the values of R WW , R WW.1 , R WW.2 , and R WW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein R WW , R WW.1 , R WW.2 , and R WW.3 correspond to R 6 , R 6.1 , R 6.2 , and R 6.3 , respectively.
  • L 1 when L 1 is substituted, L 1 is substituted with one or more first substituent groups denoted by R L1.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R L1.1 substituent group when an R L1.1 substituent group is substituted, the R L1.1 substituent group is substituted with one or more second substituent groups denoted by R L1.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R L1.2 substituent group when an R L1.2 substituent group is substituted, the R L1.2 substituent group is substituted with one or more third substituent groups denoted by R L1.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • L 1 , R L1.1 , R L1.2 , and R L1.3 have values corresponding to the values of L WW , R LWW.1 , R LWW.2 , and R LWW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein L WW , R LWW.1 , R LWW.2 , and R LWW.3 , R L1.1 , R L1.2 , and R L1.3 , respectively.
  • L 2 when L 2 is substituted, L 2 is substituted with one or more first substituent groups denoted by R L2.1 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R L2.1 substituent group when an R L2.1 substituent group is substituted, the R L2.1 substituent group is substituted with one or more second substituent groups denoted by R L2.2 as explained in the definitions section above in the description of “first substituent group(s)”.
  • R L2.2 substituent group when an R L2.2 substituent group is substituted, the R L2.2 substituent group is substituted with one or more third substituent groups denoted by R L2.3 as explained in the definitions section above in the description of “first substituent group(s)”.
  • L 2 , R L2.1 , R L2.2 , and R L2.3 have values corresponding to the values of L WW , R LWW.1 , R LWW.2 , and R LWW.3 , respectively, as explained in the definitions section above in the description of “first substituent group(s)”, wherein L WW , R LWW.1 , R LWW.2 , and R LWW.3 are L 2 , R L2.1 , R L2.2 , and R L2.3 , respectively.
  • a method of quantifying propene including (a) conducting a chemical reaction that produces propene in the presence of a gaseous internal standard at a known pressure; (b) analyzing a crude reaction mixture produced by the chemical reaction by gas chromatography; (c) measuring the signal intensities.
  • a substituted or unsubstituted dehydrogenated polyolefin In an aspect is provided a substituted or substituted dehydrogenated polyethylene or polypropylene. In an aspect the dehydrogenated polyethylene is produced by dehydrogenation of polyethylene. Alternatively, in some embodiments, the dehydrogenated polyethylene is not produced by dehydrogenation of polyethylene.
  • the dehydrogenated polyethylene is produced by installation of a leaving group followed by elimination.
  • the dehydrogenated polyethylene is produced by fragmentation of a precursor into fragments (e.g., cracking, pyrolysis, fluid catalytic cracking, catalytic cracking).
  • the dehydrogenation polyethylene comprises an olefin moiety.
  • a substituted or unsubstituted dehydrogenated polyethylene wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are unsaturated (e.g., olefinic, e.g., monoenes).
  • a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are olefinic. In embodiments, a percentage of from 0.01% to 1.5% of monomer units are olefinic. In embodiments, a percentage of from 1.7% to 2.3% of monomer units are olefinic. In embodiments, a percentage of from 1.7% to 2.3% of monomer units are olefinic. In embodiments, a percentage of from 2.4% to 4.3% of monomer units are olefinic. In embodiments, a percentage of from 4.5% to 13.2% of monomer units are olefinic.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 0.001%, at least 0.01%, at least 0.1%, at least 0.2%, at least 0.5%, at least 0.75%, at least 0.9%, at least 1%, at least 1.1%, at least 1.3%, at least 1.5%, or more. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 0.001%, at most 0.01%, at most 0.1%, at most 0.2%, at most 0.5%, at most 0.75%, at most 0.9%, at most 1%, at most 1.1%, at most 1.3%, at most 1.5%, or less.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 0.001% to about 1.5%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 0.001%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 1.5%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 0.001% to about 0.01%, about 0.001% to about 0.1%, about 0.001% to about 0.2%, about 0.001% to about 0.5%, about 0.001% to about 0.75%, about 0.001% to about 0.9%, about 0.001% to about 1%, about 0.001% to about 1.1%, about 0.001% to about 1.3%, about 0.001% to about 1.4%, about 0.001% to about 1.5%, about 0.01% to about 0.1%, about 0.01% to about 0.2%, about 0.01% to about 0.5%, about 0.01% to about 0.75%, about 0.01% to about 0.9%, about 0.01% to about 1%, about 0.01% to about 1.1%, about 0.01% to about 1.3%, about 0.01% to about 1.4%, about 0.01% to about 1.5%, about 0.1% to about 0.2%, about 0.1% to about 0.5%, about 0.1% to about 0.75%, about 0.1% to about 0.9%, about 0.01% to about 1%, about
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 0.001%, about 0.01%, about 0.1%, about 0.2%, about 0.5%, about 0.75%, about 0.9%, about 1%, about 1.1%, about 1.3%, about 1.4%, or about 1.5%. [0270] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 1.7%, at least 1.8%, at least 1.9%, at least 2.0%, at least 2.1%, at least 2.2%, at least 2.3%, or more.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 1.7%, at most 1.8%, at most 1.9%, at most 2.0%, at most 2.1%, at most 2.2%, at most 2.3%, or less. [0271] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 1.7% to about 2.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 1.7%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 2.3%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 1.7% to about 1.8%, about 1.7% to about 1.9%, about 1.7% to about 2%, about 1.7% to about 2.1%, about 1.7% to about 2.2%, about 1.7% to about 2.3%, about 1.8% to about 1.9%, about 1.8% to about 2%, about 1.8% to about 2.1%, about 1.8% to about 2.2%, about 1.8% to about 2.3%, about 1.9% to about 2%, about 1.9% to about 2.1%, about 1.9% to about 2.2%, about 1.9% to about 2.3%, about 2% to about 2.1%, about 2% to about 2.2%, about 2% to about 2.3%, about 2.1% to about 2.2%, about 2.1% to about 2.3%, or about 2.2% to about 2.3%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 1.7%, about 1.8%, about 1.9%, about 2%, about 2.1%, about 2.2%, or about 2.3%. [0272] In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 2.4%, at least 2.5%, at least 2.6%, at least 2.7%, at least 2.8%, at least 2.9%, at least 3%, at least 3.3%, at least 3.5%, at least 3.7%, at least 4%, at least 4.3%, or more.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 2.4%, at most 2.5%, at most 2.6%, at most 2.7%, at most 2.8%, at most 2.9%, at most 3%, at most 3.3%, at most 3.5%, at most 3.7%, at most 4%, at most 4.3%, or less.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 2.4% to about 4.3%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 2.4%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 4.3%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 2.4% to about 2.5%, about 2.4% to about 2.6%, about 2.4% to about 2.7%, about 2.4% to about 2.8%, about 2.4% to about 2.9%, about 2.4% to about 3%, about 2.4% to about 3.3%, about 2.4% to about 3.5%, about 2.4% to about 3.7%, about 2.4% to about 4%, about 2.4% to about 4.3%, about 2.5% to about 2.6%, about 2.5% to about 2.7%, about 2.5% to about 2.8%, about 2.5% to about 2.9%, about 2.5% to about 3%, about 2.5% to about 3.3%, about 2.5% to about 3.5%, about 2.5% to about 3.7%, about 2.5% to about 4%, about 2.5% to about 4.3%, about 2.6% to about 2.7%, about 2.6% to about 2.8%, about 2.6% to about 2.9%, about 2.6% to about 3%, about 2.6% to about 3.3%, about 2.6% to about 3.5%, about 2.6% to about 3.7%, about 2.6% to about 4%, about 2.5%
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 2.4%, about 2.5%, about 2.6%, about 2.7%, about 2.8%, about 2.9%, about 3%, about 3.3%, about 3.5%, about 3.7%, about 4%, or about 4.3%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least 4.5%, at least 4.7%, at least 5%, at least 5.2%, at least 5.5%, at least 6%, at least 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least 12%, at least 13%, at least 13.3%, or more.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most 4.5%, at most 4.7%, at most 5%, at most 5.2%, at most 5.5%, at most 6%, at most 7%, at most 8%, at most 9%, at most 10%, at most 11%, at most 12%, at most 13%, at most 13.3%, or more.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 4.5% to about 13.3%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at least about 4.5%. In embodiments, the percentage of olefinic carbon units in the dehydrogenated polyethylene is at most about 13.3%.
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 4.5% to about 4.7%, about 4.5% to about 5%, about 4.5% to about 5.2%, about 4.5% to about 5.5%, about 4.5% to about 6%, about 4.5% to about 7%, about 4.5% to about 8%, about 4.5% to about 9%, about 4.5% to about 10%, about 4.5% to about 12%, about 4.5% to about 13.3%, about 4.7% to about 5%, about 4.7% to about 5.2%, about 4.7% to about 5.5%, about 4.7% to about 6%, about 4.7% to about 7%, about 4.7% to about 8%, about 4.7% to about 9%, about 4.7% to about 10%, about 4.7% to about 12%, about 4.7% to about 13.3%, about 5% to about 5.2%, about 5% to about 5.5%, about 5% to about 6%, about 5% to about 7%, about 5% to about 8%, about 5% to about 9%, about 5% to about 10%, about 5% to about 12%, about 5% to about
  • the percentage of olefinic carbon units in the dehydrogenated polyethylene is about 4.5%, about 4.7%, about 5%, about 5.2%, about 5.5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 12%, or about 13.3%.
  • a substituted or unsubstituted dehydrogenated polyethylene wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of repeating ethylene units of a polymer are olefinic.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is at least 0.62%, at least 0.81%, at least 1.06%, at least 1.09%, at least 1.34%, at least 1.42%, at least 1.46%, at least 1.76%, at least 2.17%, at least 2.3%, at least 2.38%, at least 2.55%, at least 3.54%, or more.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is at most 0.62%, at most 0.81%, at most 1.06%, at most 1.09%, at most 1.34%, at most 1.42%, at most 1.46%, at most 1.76%, at most 2.17%, at most 2.3%, at most 2.38%, at most 2.55%, at most 3.54%, or less. [0277] In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 2.38 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.1 %.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 2.38 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 0.62 %, about 0.1 % to about 0.81 %, about 0.1 % to about 1.06 %, about 0.1 % to about 1.09 %, about 0.1 % to about 1.34 %, about 0.1 % to about 1.42 %, about 0.1 % to about 1.46 %, about 0.1 % to about 1.76 %, about 0.1 % to about 2.17 %, about 0.1 % to about 2.3 %, about 0.1 % to about 2.38 %, about 0.62 % to about 0.81 %, about 0.62 % to about 1.06 %, about 0.62 % to about 1.09 %, about 0.62 % to about 1.34 %, about 0.62 % to about 1.42 %, about 0.62 % to about
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 %, about 0.62 %, about 0.81 %, about 1.06 %, about 1.09 %, about 1.34 %, about 1.42 %, about 1.46 %, about 1.76 %, about 2.17 %, about 2.3 %, or about 2.38 %.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.1 %.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 0.62 %, about 0.1 % to about 0.81 %, about 0.1 % to about 1.34 %, about 0.1 % to about 1.09 %, about 0.1 % to about 1.34 %, about 0.1 % to about 1.76 %, about 0.1 % to about 2.38 %, about 0.1 % to about 2.55 %, about 0.1 % to about 3.54 %, about 0.1 % to about 4 %, about 0.1 % to about 10 %, about 0.62 % to about 0.81 %, about 0.62 % to about 1.34 %, about 0.62 % to about 1.09 %, about 0.62 % to about 1.34 %, about 0.62 % to about 1.76 %, about 0.62 % to about 2.38
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 %, about 0.62 %, about 0.81 %, about 1.34 %, about 1.09 %, about 1.34 %, about 1.76 %, about 2.38 %, about 2.55 %, about 3.54 %, about 4 %, or about 10 %.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 20 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.1 %.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 20 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 % to about 1 %, about 0.1 % to about 1.5 %, about 0.1 % to about 1.75 %, about 0.1 % to about 2 %, about 0.1 % to about 2.5 %, about 0.1 % to about 3 %, about 0.1 % to about 4 %, about 0.1 % to about 5 %, about 0.1 % to about 7.5 %, about 0.1 % to about 10 %, about 0.1 % to about 20 %, about 1 % to about 1.5 %, about 1 % to about 1.75 %, about 1 % to about 2 %, about 1 % to about 2.5 %, about 1 % to about 3 %, about 1 % to about 4 %, about 1 % to about 5 %, about 1 % to about
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.1 %, about 1 %, about 1.5 %, about 1.75 %, about 2 %, about 2.5 %, about 3 %, about 4 %, about 5 %, about 7.5 %, about 10 %, or about 20 %.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.01%, at least about 0.05%, at least about 0.1%, at least about 0.15%, at least about 0.17%, at least about 0.19%, at least about 0.2%, at least about 0.22%, at least about 0.25%, at least about 0.3%, at least about 0.35%, at least about 0.38%, at least about 0.4%, at least about 0.45%, at least about 0.5%, at least about 0.52%, at least about 0.55%, at least about 0.56, at least about 0.6%, at least about 0.65%, at least about 0.75%, at least about 1%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 10%, or more.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 0.01%, at most about 0.05%, at most about 0.1%, at most about 0.15%, at most about 0.17%, at most about 0.19%, at most about 0.2%, at most about 0.22%, at most about 0.25%, at most about 0.3%, at most about 0.35%, at most about 0.38%, at most about 0.4%, at most about 0.45%, at most about 0.5%, at most about 0.52%, at most about 0.55%, at most about 0.56, at most about 0.6%, at most about 0.65%, at most about 0.75%, at most about 1%, at most about 2%, at most about 3%, at most about 4%, at most about 5%, at most about 10%, or less.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.01 % to about 10 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at least about 0.01 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polyethylene is at most about 10 %.
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.01 % to about 0.05 %, about 0.01 % to about 0.1 %, about 0.01 % to about 0.19 %, about 0.01 % to about 0.22 %, about 0.01 % to about 0.25 %, about 0.01 % to about 0.38 %, about 0.01 % to about 0.52 %, about 0.01 % to about 0.56 %, about 0.01 % to about 1 %, about 0.01 % to about 2 %, about 0.01 % to about 10 %, about 0.05 % to about 0.1 %, about 0.05 % to about 0.19 %, about 0.05 % to about 0.22 %, about 0.05 % to about 0.25 %, about 0.05 % to about 0.38 %, about 0.05 % to about 0.52 %, about 0.05 % to about 0.56 %, about 0.05 % to about 1 %, about 0.05 % to about
  • the percentage of olefinic carbons in the dehydrogenated polyethylene is about 0.01 %, about 0.05 %, about 0.1 %, about 0.19 %, about 0.22 %, about 0.25 %, about 0.38 %, about 0.52 %, about 0.56 %, about 1 %, about 2 %, or about 10 %.
  • a substituted or unsubstituted dehydrogenated polyethylene having a number average molecular weight of 2,200 Da or greater.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 500,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 300,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 200,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 100,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 40,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 20,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 1,000 Da to about 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 500,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 300,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 200,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 100,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 40,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 20,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from about 2,200 Da to about 6,500 Da or a number average molecular weight greater than about 6,700 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 500,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 300,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 200,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 100,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 40,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 20,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 1,000 Da to 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 500,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 400,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 300,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 200,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 100,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 50,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 40,000 Da.
  • the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 30,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 20,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 10,000 Da. In embodiments, the substituted or unsubstituted dehydrogenated polyethylene has a number average molecular weight of from 2,200 Da to 6,500 Da or a number average molecular weight greater than 6,700 Da.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 0.5 kDa, at least about 1 kDa, at least about 2 kDa, at least about 4 kDa, at least about 5 kDa, at least about 5.22 kDa, at least about 6 kDa, at least about 7 kDa, at least about 8 kDa, at least about 9 kDa, at least about 10 kDa, at least about 11 kDa, at least about 12 kDa, at least about 13 kDa, at least about 14 kDa, at least about 15 kDa, at least about 16 kDa, at least about 17 kDa, at least about 18 kDa, at least about 18.2 kDa, at least about 19 kDa, at least about 20 kDa, at least about 21 kDa, at least about 25 kDa, at least about
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 0.5 kDa, at most about 1 kDa, at most about 2 kDa, at most about 4 kDa, at most about 5 kDa, at most about 5.22 kDa, at most about 6 kDa, at most about 7 kDa, at most about 8 kDa, at most about 9 kDa, at most about 10 kDa, at most about 11 kDa, at most about 12 kDa, at most about 13 kDa, at most about 14 kDa, at most about 15 kDa, at most about 16 kDa, at most about 17 kDa, at most about 18 kDa, at most about 18.2 kDa, at most about 19 kDa, at most about 20 kDa, at most about 21 kDa, at most about 25
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 5.22 kDa, or at least about 18.2 kDa, more more. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 5.22 kDa, or at least about 18.2 kDa, or less. [0290] In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 2 kDa to about 50 kDa.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 2 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 50 kDa.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 2 kDa to about 4 kDa, about 2 kDa to about 5 kDa, about 2 kDa to about 5.22 kDa, about 2 kDa to about 8 kDa, about 2 kDa to about 10 kDa, about 2 kDa to about 12 kDa, about 2 kDa to about 15 kDa, about 2 kDa to about 18.2 kDa, about 2 kDa to about 20 kDa, about 2 kDa to about 35 kDa, about 2 kDa to about 50 kDa, about 4 kDa to about 5 kDa, about 4 kDa to about 5.22 kDa, about 4 kDa to about 8 kDa, about 4 kDa to about 10 kDa, about 4 kDa to about 12 kDa
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 2 kDa, about 4 kDa, about 5 kDa, about 5.22 kDa, about 8 kDa, about 10 kDa, about 12 kDa, about 15 kDa, about 18.2 kDa, about 20 kDa, about 35 kDa, or about 50 kDa.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 0.5 kDa, at least about 1 kDa, at least about 1.23 kDa, at least about 1.67 kDa, at least about 2 kDa, at least about 2.24 kDa, at least about 3 kDa, at least about 3.9 kDa, at least about 4 kDa, at least about 4.07 kDa, at least about 5 kDa, at least about 5.22 kDa, at least about 6 kDa, at least about 7 kDa, at least about 8 kDa, at least about 9 kDa, at least about 10 kDa, at least about 11 kDa, at least about 12 kDa, at least about 13 kDa, at least about 14 kDa, at least about 15 kDa, at least about 16 kDa, at least about 17 kDa
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 0.5 kDa, at most about 1 kDa, at most about 1.23 kDa, at most about 1.67 kDa, at most about 2 kDa, at most about 2.24 kDa, at most about 3 kDa, at most about 3.9 kDa, at most about 4 kDa, at most about 4.07 kDa, at most about 5 kDa, at most about 5.22 kDa, at most about 6 kDa, at most about 7 kDa, at most about 8 kDa, at most about 9 kDa, at most about 10 kDa, at most about 11 kDa, at most about 12 kDa, at most about 13 kDa, at most about 14 kDa, at most about 15 kDa, at most about 16 kDa,
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 0.5 kDa to about 50 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at least about 0.5 kDa. In embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is at most about 50 kDa.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 0.5 kDa to about 1 kDa, about 0.5 kDa to about 1.23 kDa, about 0.5 kDa to about 1.67 kDa, about 0.5 kDa to about 2 kDa, about 0.5 kDa to about 2.24 kDa, about 0.5 kDa to about 3 kDa, about 0.5 kDa to about 3.9 kDa, about 0.5 kDa to about 4.07 kDa, about 0.5 kDa to about 5.22 kDa, about 0.5 kDa to about 10 kDa, about 0.5 kDa to about 50 kDa, about 1 kDa to about 1.23 kDa, about 1 kDa to about 1.67 kDa, about 1 kDa to about 2 kDa, about 1 kDa to about 2.24
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polyethylene is about 0.5 kDa, about 1 kDa, about 1.23 kDa, about 1.67 kDa, about 2 kDa, about 2.24 kDa, about 3 kDa, about 3.9 kDa, about 4.07 kDa, about 5.22 kDa, about 10 kDa, or about 50 kDa.
  • the polydispersity of the dehydrogenated polyethylene is at least about 1.001, at least about 1.01, at least about 1.05, at least about 1.1, at least about 1.25, at least about 1.5, at least about 1.6, at least about 1.7, at least about 1.75, at least about 1.8, at least about 1.84, at least about 1.9, at least about 2, at least about 2.1, at least about 2.25, at least about 2.5, at least about 2.75, at least about 3, at least about 3.25, at least about 3.35, at least about 3.4, at least about 3.45, at least about 3.48, at least about 3.5, at least about 3.55, at least about 3.75, at least about 4, at least about 4.25, at least about 4.5, at least about 4.75, at least about 5, or more.
  • the polydispersity of the dehydrogenated polyethylene is at most about 1.001, at most about 1.01, at most about 1.05, at most about 1.1, at most about 1.25, at most about 1.5, at most about 1.6, at most about 1.7, at most about 1.75, at most about 1.8, at most about 1.84, at most about 1.9, at most about 2, at most about 2.1, at most about 2.25, at most about 2.5, at most about 2.75, at most about 3, at most about 3.25, at most about 3.35, at most about 3.4, at most about 3.45, at most about 3.48, at most about 3.5, at most about 3.55, at most about 3.75, at most about 4, at most about 4.25, at most about 4.5, at most about 4.75, at most about 5, or less.
  • the polydispersity of the dehydrogenated polyethylene is about 1.1 to about 8. In embodiments, the polydispersity of the dehydrogenated polyethylene is at least about 1.1. In embodiments, the polydispersity of the dehydrogenated polyethylene is at most about 8.
  • the polydispersity of the dehydrogenated polyethylene is about 1.1 to about 1.3, about 1.1 to about 1.5, about 1.1 to about 1.7, about 1.1 to about 1.8, about 1.1 to about 1.84, about 1.1 to about 1.9, about 1.1 to about 2.5, about 1.1 to about 3.25, about 1.1 to about 3.48, about 1.1 to about 5, about 1.1 to about 8, about 1.3 to about 1.5, about 1.3 to about 1.7, about 1.3 to about 1.8, about 1.3 to about 1.84, about 1.3 to about 1.9, about 1.3 to about 2.5, about 1.3 to about 3.25, about 1.3 to about 3.48, about 1.3 to about 5, about 1.3 to about 8, about 1.5 to about 1.7, about 1.5 to about 1.8, about 1.5 to about 1.84, about 1.5 to about 1.9, about 1.5 to about 2.5, about 1.5 to about 3.25, about 1.5 to about 3.48, about 1.5 to about 5, about 1.5 to about 8, about 1.7 to about 1.8, about 1.7 to about 1.84, about 1.5 to about 1.9, about 1.5 to
  • the polydispersity of the dehydrogenated polyethylene is about 1.1, about 1.3, about 1.5, about 1.7, about 1.8, about 1.84, about 1.9, about 2.5, about 3.25, about 3.48, about 5, or about 8. [0297] In embodiments, a percentage of from about 0.01% to about 11% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 0.01% to about 10% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of from about 2.4% to about 4.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 4.5% to about 13.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1% to about 3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.5% to about 3% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of about 1.9% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.7% to about 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from about 1.9% to about 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of about 1.7% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 1.8% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 1.9% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of about 2.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of about 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. [0298] In embodiments, a percentage of from 0.01% to 11% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 0.01% to 10% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of from 0.01% to 9% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 0.01% to 8% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 8% or less of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 0.01% to 1.5% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of from 2.4% to 4.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 4.5% to 13.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1% to 3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.5% to 3% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of 1.9% of monomer units of the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.7% to 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.7% to 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of from 1.9% to 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 1.7% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of 1.8% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 1.9% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 2.1% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated. In embodiments, a percentage of 2.2% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • a percentage of 2.3% of monomer units in the substituted or unsubstituted dehydrogenated polyethylene are unsaturated.
  • the percentage of aromatic carbons in the dehydrogenated polyethylene is at least about 0%, at least about 0.0001%, at least about 0.001%, at least about 0.01%, at least about 0.02%, at least about 0.03%, at least about 0.04%, at least about 0.05%, at least about 0.06%, at least about 0.07%, at least about 0.08%, at least about 0.09, at least about 0.1%, at least about 0.11%, at least about 0.12%, at least about 0.13%, at least about 0.14%, at least about 0.15%, at least about 0.16%, at least about 0.17%, at least about 0.18%, at least about 0.19%, at least about 0.2%, at least about 0.22%, at least about 0.24%, at least about 0.26%, at least about 0.28%, at least about 0.3%, at least about 0.3
  • the percentage of aromatic carbons in the dehydrogenated polyethylene is at most about 0%, at most about 0.0001%, at most about 0.001%, at most about 0.01%, at most about 0.02%, at most about 0.03%, at most about 0.04%, at most about 0.05%, at most about 0.06%, at most about 0.07%, at most about 0.08%, at most about 0.09, at most about 0.1%, at most about 0.11%, at most about 0.12%, at most about 0.13%, at most about 0.14%, at most about 0.15%, at most about 0.16%, at most about 0.17%, at most about 0.18%, at most about 0.19%, at most about 0.2%, at most about 0.22%, at most about 0.24%, at most about 0.26%, at most about 0.28%, at most about 0.3%, at most about 0.32%, at most about 0.33%, at most about 0.34%, at most about 0.35%, at most about 0.4%, at most about 0.5%, at most about 0.4%, at most about
  • the percentage of aromatic carbons in the dehydrogenated polyethylene is about 0.001 % to about 10 %. In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is at least about 0.001 %. In some embodiments, the percentage of aromatic carbons in the dehydrogenated polyethylene is at most about 10 %.
  • the percentage of aromatic carbons in the dehydrogenated polyethylene is about 0.001 % to about 0.01 %, about 0.001 % to about 0.02 %, about 0.001 % to about 0.04 %, about 0.001 % to about 0.08 %, about 0.001 % to about 0.09 %, about 0.001 % to about 0.1 %, about 0.001 % to about 0.11 %, about 0.001 % to about 0.33 %, about 0.001 % to about 0.47 %, about 0.001 % to about 1.47 %, about 0.001 % to about 10 %, about 0.01 % to about 0.02 %, about 0.01 % to about 0.04 %, about 0.01 % to about 0.08 %, about 0.01 % to about 0.09 %, about 0.01 % to about 0.1 %, about 0.01 % to about 0.11 %, about 0.01 % to about 0.33 %, about 0.01 % to about 0.47
  • the percentage of aromatic carbons in the dehydrogenated polyethylene is about 0.001 %, about 0.01 %, about 0.02 %, about 0.04 %, about 0.08 %, about 0.09 %, about 0.1 %, about 0.11 %, about 0.33 %, about 0.47 %, about 1.47 %, or about 10 %.
  • the distribution of unsaturated monomer units in the substituted or unsubstituted dehydrogenated polyethylene is irregular.
  • the dehydrogenated polyethylene is produced from an HDPE precursor.
  • the HDPE precursor has a number average molecular weight of at least about 0.5 kDa, at least about 1 kDa, at least about 2 kDa, at least about 5 kDa, at least about 10 kDa, at least about 15 kDa, at least about 20 kDa, at least about 22.5 kDa, at least about 25 kDa, at least about 26.1 kDa, at least about 37.5 kDa, at least about 30 kDa, at least about 32.5 kDa, at least about 35 kDa, at least about 37.5 kDa, at least about 40 kDa, at least about 42.5 kDa, at least about 45 kDa, at least about 50 kDa, at least about 55 kDa, at least about 60 kDa, at least about 65 kDa, at least about 75 kDa, at least about 90 kDa, at least about 100 kDa, or more.
  • the HDPE precursor has a number average molecular weight of at most about 0.5 kDa, at most about 1 kDa, at most about 2 kDa, at most about 5 kDa, at most about 10 kDa, at most about 15 kDa, at most about 20 kDa, at most about 22.5 kDa, at most about 25 kDa, at most about 26.1 kDa, at most about 37.5 kDa, at most about 30 kDa, at most about 32.5 kDa, at most about 35 kDa, at most about 37.5 kDa, at most about 40 kDa, at most about 42.5 kDa, at most about 45 kDa, at most about 50 kDa, at most about 55 kDa, at most about 60 kDa, at most about 65 kDa, at most about 75 kDa, at most about 90 kDa, at most about 100 kDa, or
  • the number average molecular weight of the HDPE precursor is about 0.5 kDa to about 100 kDa. In embodiments, the number average molecular weight of the HDPE precursor is at least about 0.5 kDa. In embodiments, the number average molecular weight of the HDPE precursor is at most about 100 kDa.
  • the number average molecular weight of the HDPE precursor is about 0.5 kDa to about 1 kDa, about 0.5 kDa to about 5 kDa, about 0.5 kDa to about 10 kDa, about 0.5 kDa to about 15 kDa, about 0.5 kDa to about 20 kDa, about 0.5 kDa to about 25 kDa, about 0.5 kDa to about 26.1 kDa, about 0.5 kDa to about 30 kDa, about 0.5 kDa to about 35 kDa, about 0.5 kDa to about 50 kDa, about 0.5 kDa to about 100 kDa, about 1 kDa to about 5 kDa, about 1 kDa to about 10 kDa, about 1 kDa to about 15 kDa, about 1 kDa to about 20 kDa, about 1 kDa to about 25 kDa, about 1
  • the number average molecular weight of the HDPE precursor is about 0.5 kDa, about 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 25 kDa, about 26.1 kDa, about 30 kDa, about 35 kDa, about 50 kDa, or about 100 kDa.
  • the dehydrogenated polyethylene is produced from an LDPE precursor.
  • the LDPE precursor has a number average molecular weight of at most about 0.5 kDa, at most about 1 kDa, at most about 2 kDa, at most about 5 kDa, at most about 10 kDa, at most about 15 kDa, at most about 20 kDa, at most about 22.5 kDa, at most about 25 kDa, at most about 26.1 kDa, at most about 30 kDa, at most about 32.5 kDa, at most about 35.1 kDa, at most about 37.5 kDa, at most about 30 kDa, at most about 32.5 kDa, at most about 35 kDa, at most about 37.5 kDa, at most about 40 kDa, at most about 42.5 kDa, at most about 45 kDa, at most about 50 kDa, at most about 55 kDa, at most about 60 kDa, at most about 65 kD
  • the number average molecular weight of the LDPE precursor is about 1 kDa to about 100 kDa. In embodiments, the number average molecular weight of the LDPE precursor is at least about 1 kDa. In embodiments, the number average molecular weight of the LDPE precursor is at most about 100 kDa.
  • the number average molecular weight of the LDPE precursor is about 1 kDa to about 5 kDa, about 1 kDa to about 10 kDa, about 1 kDa to about 15 kDa, about 1 kDa to about 20 kDa, about 1 kDa to about 25 kDa, about 1 kDa to about 30 kDa, about 1 kDa to about 32.5 kDa, about 1 kDa to about 35.1 kDa, about 1 kDa to about 37.5 kDa, about 1 kDa to about 50 kDa, about 1 kDa to about 100 kDa, about 5 kDa to about 10 kDa, about 5 kDa to about 15 kDa, about 5 kDa to about 20 kDa, about 5 kDa to about 25 kDa, about 5 kDa to about 30 kDa, about 5 kDa to about 32.5
  • the number average molecular weight of the LDPE precursor is about 1 kDa, about 5 kDa, about 10 kDa, about 15 kDa, about 20 kDa, about 25 kDa, about 30 kDa, about 32.5 kDa, about 35.1 kDa, about 37.5 kDa, about 50 kDa, or about 100 kDa.
  • the dehydrogenated polyethylene is produced from LLDPE.
  • a dehydrogenated polypropylene is substituted or unsubstituted.
  • the dehydrogenated polyethylene is produced by dehydrogenation of polypropylene.
  • the dehydrogenated polypropylene is not produced by dehydrogenation of polypropylene.
  • the dehydrogenated polypropylene is produced by installation of a leaving group on polypropylene followed by elimination.
  • the dehydrogenated polypropylene is produced by fragmentation of a precursor into fragments (e.g., cracking, pyrolysis, fluid catalytic cracking, catalytic cracking).
  • the dehydrogenated polypropylene comprises an olefin moiety.
  • the dehydrogenated polypropylene comprises a trisubstituted olefin. In some embodiments, the dehydrogenated polypropylene comprises a disubsituted olefin. In some embodiments, the dehydrogenated polypropylene comprises a 1,1-disubstitued olefin. In some embodiments, the dehydrogenated polypropylene comprises a 1,1-disubstitued olefin or a trisubsituted olefin. In some embodiments, the dehydrogenated polypropylene comprises a 1,1-disubstitued olefin or a trisubsituted olefin.
  • the dehydrogenated polypropylene comprises a 1,1- disubstitued olefin and a trisubsituted olefin.
  • the percentage of olefinic carbons in the dehydrogenated polypropylene is at least about 0.01%, at least about 0.02%, at least about 0.05%, at least about 0.07%, at least about 0.1%, at least about 0.2%, at least about 0.5%, at least about 0.75%, at least about 1%%, at least about 1.51%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 5.33%, at least about 6%, at least about 7%, at least about 7.5%, at least about 7.97%, at least about 8%, at least about 8.5%, at least about 8.85%, at least about 9%, at least about 9.5%, at least about 10%, at least about 10.09%, at least about 10.5%, at least about 11%, at least
  • the percentage of olefinic carbons in the dehydrogenated polypropylene is at most about 0.01%, at most about 0.02%, at most about 0.05%, at most about 0.07%, at most about 0.1%, at most about 0.2%, at most about 0.5%, at most about 0.75%, at most about 1%, at most about 1.51%, at most about 2%, at most about 3%, at most about 4%, at most about 5%, at most about 5.33%, at most about 6%, at most about 7%, at most about 7.5%, at most about 7.97%, at most about 8%, at most about 8.5%, at most about 8.85%, at most about 9%, at most about 9.5%, at most about 10%, at most about 10.09%, at most about 10.5%, at most about 11%, at most about 11.5%, at most about 12%, at most about 12%, at most about 13%, at most about 14%, at most about 15%, at most about 17.5%, at most about 20%, at most about 30%
  • the percentage of olefinic carbons in the dehydrogenated polypropylene is about 0.1 % to about 25 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polypropylene is at least about 0.1 %. In some embodiments, the percentage of olefinic carbons in the dehydrogenated polypropylene is at most about 25 %.
  • the percentage of olefinic carbons in the dehydrogenated polypropylene is about 0.1 % to about 1 %, about 0.1 % to about 1.51 %, about 0.1 % to about 3 %, about 0.1 % to about 4 %, about 0.1 % to about 5.33 %, about 0.1 % to about 6.5 %, about 0.1 % to about 7.97 %, about 0.1 % to about 8.85 %, about 0.1 % to about 10.09 %, about 0.1 % to about 15 %, about 0.1 % to about 25 %, about 1 % to about 1.51 %, about 1 % to about 3 %, about 1 % to about 4 %, about 1 % to about 5.33 %, about 1 % to about 6.5 %, about 1 % to about 7.97 %, about 1 % to about 8.85 %, about 1 % to about 10.09 %, about 1 % to about 15 %, about 1 % to about 1 % to
  • the percentage of olefinic carbons in the dehydrogenated polypropylene is about 0.1 %, about 1 %, about 1.51 %, about 3 %, about 4 %, about 5.33 %, about 6.5 %, about 7.97 %, about 8.85 %, about 10.09 %, about 15 %, or about 25 %.
  • the percentage of monomer units comprising internal (e.g., trisubstituted) olefins in the dehydrogenated polypropylene is at least about 0.01%, at least about 0.02%, at least about 0.05%, at least about 0.07%, at least about 0.1%, at least about 0.2%, at least about 0.5%, at least about 0.75%, at least about 1%%, at least about 1.51%, at least about 2%, at least about 3%, at least about 4%, at least about 5%, at least about 5.92%, at least about 6%, at least about 6.7%, at least about 7%, at least about 7.5%, at least about 8%, at least about 8.5%, at least about 9%, at least about 9.23%, at least about 9.5%, at least about 10%, at least about 10.5%, at least about 11%, at least about 11.5%, at least about 12%, at least about 12%, at least about 13%, at least about 14%, at least about 15%, at least about
  • the percentage of monomer units comprising internal (e.g., trisubstituted) olefins in the dehydrogenated polypropylene is at most about 0.01%, at most about 0.02%, at most about 0.05%, at most about 0.07%, at most about 0.1%, at most about 0.2%, at most about 0.5%, at most about 0.75%, at most about 1%%, at most about 1.51%, at most about 2%, at most about 3%, at most about 4%, at most about 5%, at most about 5.92%, at most about 6%, at most about 6.7%, at most about 7%, at most about 7.5%, at most about 8%, at most about 8.5%, at most about 9%, at most about 9.23%, at most about 9.5%, at most about 10%, at most about 10.5%, at most about 11%, at most about 11.5%, at most about 12%, at most about 12%, at most about 13%, at most about
  • the percentage of monomer units comprising internal (e.g., trisubstituted) olefins in the dehydrogenated polypropylene is about 0.1 % to about 30 %. In some embodiments, the percentage of monomer units comprising internal (e.g., trisubstituted) olefins in the dehydrogenated polypropylene is at least about 0.1 %. In some embodiments, the percentage of monomer units comprising internal (e.g., trisubstituted) olefins in the dehydrogenated polypropylene is at most about 30 %.
  • the percentage of monomer units comprising internal (e.g., trisubstituted) olefins in the dehydrogenated polypropylene is about 0.1 % to about 1 %, about 0.1 % to about 2 %, about 0.1 % to about 3 %, about 0.1 % to about 5 %, about 0.1 % to about 5.92 %, about 0.1 % to about 6.7 %, about 0.1 % to about 7.5 %, about 0.1 % to about 8.5 %, about 0.1 % to about 9.23 %, about 0.1 % to about 15 %, about 0.1 % to about 30 %, about 1 % to about 2 %, about 1 % to about 3 %, about 1 % to about 5 %, about 1 % to about 5.92 %, about 1 % to about 6.7 %, about 1 % to about 7.5 %, about 1 % to about 8.5 %, about 1 % to about 9.23 %,
  • the percentage of monomer units comprising internal (e.g., trisubstituted) olefins in the dehydrogenated polypropylene is about 0.1 %, about 1 %, about 2 %, about 3 %, about 5 %, about 5.92 %, about 6.7 %, about 7.5 %, about 8.5 %, about 9.23 %, about 15 %, or about 30 %.
  • the percentage of monomer units comprising terminal (e.g., 1,1- disubstituted) olefins in the dehydrogenated polypropylene is at least about 0.01%, at least about 0.02%, at least about 0.05%, at least about 0.07%, at least about 0.1%, at least about 0.2%, at least about 0.5%, at least about 0.75%, at least about 0.86%, at least about 1%, at least about 1.25%, at least about 1.5%, at least about 1.75%, at least about 2%, at least about 2.05%, at least about 2.1%, at least about 2.15%, at least about 2.25%, at least about 2.5%, at least about 2.75%, at least about 3%, at least about 4%, at least about 5%, at least about 6%, at least about 7%, at least about 7.5%, at least about 8%, at least about 8.5%, at least about 9%, at least about 9.5%, at least about 10%, at least about 10.5%, at least
  • the percentage of monomer units comprising terminal (e.g., 1,1- disubstituted) olefins in the dehydrogenated polypropylene is at most about 0.01%, at most about 0.02%, at most about 0.05%, at most about 0.07%, at most about 0.1%, at most about 0.2%, at most about 0.5%, at most about 0.75%, at most about 0.86%, at most about 1%, at most about 1.25%, at most about 1.5%, at most about 1.75%, at most about 2%, at most about 2.05%, at most about 2.1%, at most about 2.15%, at most about 2.25%, at most about 2.5%, at most about 2.75%, at most about 3%, at most about 4%, at most about 5%, at most about 6%, at most about 7%, at most about 7.5%, at most about 8%, at most about 8.5%, at most about 9%, at most about 9.5%, at most about 10%, at most about 10.5%, at most
  • the percentage of monomer units comprising terminal (e.g., 1,1- disubstituted) olefins in the dehydrogenated polypropylene is about 0.1 % to about 20 %. In some embodiments, the percentage of monomer units comprising terminal (e.g., 1,1- disubstituted) olefins in the dehydrogenated polypropylene is at least about 0.1 %. In some embodiments, the percentage of monomer units comprising terminal (e.g., 1,1-disubstituted) olefins in the dehydrogenated polypropylene is at most about 20 %.
  • the percentage of monomer units comprising terminal (e.g., 1,1-disubstituted) olefins in the dehydrogenated polypropylene is about 0.1 % to about 0.5 %, about 0.1 % to about 0.86 %, about 0.1 % to about 1 %, about 0.1 % to about 1.5 %, about 0.1 % to about 1.75 %, about 0.1 % to about 2.05 %, about 0.1 % to about 2.15 %, about 0.1 % to about 2.5 %, about 0.1 % to about 3 %, about 0.1 % to about 5 %, about 0.1 % to about 20 %, about 0.5 % to about 0.86 %, about 0.5 % to about 1 %, about 0.5 % to about 1.5 %, about 0.5 % to about 1.75 %, about 0.5 % to about 2.05 %, about 0.5 % to about 2.15 %, about 0.5 % to about 2.5 %,
  • the percentage of monomer units comprising terminal (e.g., 1,1-disubstituted) olefins in the dehydrogenated polypropylene is about 0.1 %, about 0.5 %, about 0.86 %, about 1 %, about 1.5 %, about 1.75 %, about 2.05 %, about 2.15 %, about 2.5 %, about 3 %, about 5 %, or about 20 %.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polypropylene is at least about 0.5 kDa, at least about 0.75 kDa, at least about 1 kDa, at least about 1.5 kDa, at least about 1.75 kDa, at least about 2 kDa, at least about 2.25 kDa, at least about 2.41 kDa, at least about 2.5 kDa, at least about 2.75 kDa, at least about 3 kDa, at least about 4 kDa, at least about 5 kDa, at least about 10 kDa, at least about 20 kDa, at least about 30 kDa, at least about 40 kDa, at least about 50 kDa, at least about 75 kDa, at least about 100 kDa, at least about 250 kDa, at least about 500 kDa, or more.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polypropylene is at most about 0.5 kDa, at most about 0.75 kDa, at most about 1 kDa, at most about 1.5 kDa, at most about 1.75 kDa, at most about 2 kDa, at most about 2.25 kDa, at most about 2.41 kDa, at most about 2.5 kDa, at most about 2.75 kDa, at most about 3 kDa, at most about 4 kDa, at most about 5 kDa, at most about 10 kDa, at most about 20 kDa, at most about 30 kDa, at most about 40 kDa, at most about 50 kDa, at most about 75 kDa, at most about 100 kDa, at most about 250 kDa, at most about 500 kDa, or more.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polypropylene is about 0.5 kDa to about 500 kDa. In some embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polypropylene is at least about 0.5 kDa. In some embodiments, the number average molecular weight of the substituted or unsubstituted dehydrogenated polypropylene is at most about 500 kDa.
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polypropylene is about 0.5 kDa to about 1 kDa, about 0.5 kDa to about 1.5 kDa, about 0.5 kDa to about 1.75 kDa, about 0.5 kDa to about 2 kDa, about 0.5 kDa to about 2.25 kDa, about 0.5 kDa to about 2.41 kDa, about 0.5 kDa to about 3 kDa, about 0.5 kDa to about 5 kDa, about 0.5 kDa to about 10 kDa, about 0.5 kDa to about 50 kDa, about 0.5 kDa to about 500 kDa, about 1 kDa to about 1.5 kDa, about 1 kDa to about 1.75 kDa, about 1 kDa to about 2 kDa, about 1 kDa to about 2.25 k
  • the number average molecular weight of the substituted or unsubstituted dehydrogenated polypropylene is about 0.5 kDa, about 1 kDa, about 1.5 kDa, about 1.75 kDa, about 2 kDa, about 2.25 kDa, about 2.41 kDa, about 3 kDa, about 5 kDa, about 10 kDa, about 50 kDa, or about 500 kDa.
  • a reaction vessel comprising: (a) a dehydrogenated polymer; (b) one or more isomerization catalysts; and (c) one or more metathesis catalysts.
  • the reaction vessel further includes an exogenously added olefin.
  • the exogenously added olefin is ethylene.
  • Embodiment 1 A method of degrading a substance, said method comprising: (i) conducting one or more reaction(s) to form one or more olefin units in the substance; (ii) subjecting, after step (i), to conditions for olefin metathesis; and (iii) subjecting, after step (i), to conditions for olefin isomerization. [0327] Embodiment 2. The method of embodiment 1, wherein step (i) comprises subjecting the substance to conditions for dehydrogenation. [0328] Embodiment 3.
  • a method of making a substituted or unsubstituted alkene comprising subjecting a dehydrogenated polymer to conditions for metathesis and to conditions for olefin isomerization.
  • Embodiment 4 A method of making a substituted or unsubstituted alkene, said method comprising subjecting a first substance to conditions for olefin metathesis and to conditions for olefin isomerization; wherein: (i) said first substance comprises at least 20 carbon atoms per molecule; or (ii) prior to subjecting said first substance to conditions for olefin metathesis and to conditions for olefin isomerization, the method comprises subjecting a second substance to conditions for dehydrogenation, thereby forming said first substance.
  • Embodiment 5 The method of one of embodiments 3 to 4, wherein the substituted or unsubstituted alkene is a substituted or unsubstituted propene.
  • Embodiment 6 The method of one of embodiments 4 to 5, wherein said first substance is a substituted or unsubstituted dehydrogenated polyethylene.
  • a method of making an alkene comprising mixing a dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s); wherein: (i) the dehydrogenated polymer comprises at least 20 carbon atoms; or (ii) prior to said mixing, the method comprises mixing a polymer with one or more dehydrogenating reagent(s), thereby forming said dehydrogenated polymer.
  • a method of making a dehydrogenated polymer comprising mixing a polymer with one or more dehydrogenating reagent(s), wherein (i) a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or 4.5% to 13.2% of monomer units in the dehydrogenated polymer are unsaturated; (ii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da or greater; (iii) the dehydrogenated polymer has a number average molecular weight of about 2,200 Da to about 6,500 Da and a percentage of from 0.01% to 10% of monomer units are unsaturated; or (iv) the dehydrogenated polymer has a number average molecular weight of about 1,000 Da to about 500,000 Da and a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 10% of monomer units in the dehydrogenated polymer are unsaturated.
  • Embodiment 9 The method of embodiment 8, wherein the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da or from about 6,700 Da to about 15,000 Da.
  • Embodiment 10 The method of embodiment 8, wherein the dehydrogenated polymer has a number average molecular weight of from about 2,200 Da to about 6,500 Da.
  • Embodiment 11 The method of one of embodiments 8 to 10, further comprising mixing the dehydrogenated polymer with one or more olefin metathesis reagent(s) and one or more isomerization reagent(s), thereby forming an alkene.
  • Embodiment 13 The method of one of embodiments 7 to 11, wherein the dehydrogenated polymer is a substituted or unsubstituted dehydrogenated polyethylene.
  • Embodiment 13 The method of one of embodiments 7 to 11, wherein the alkene is a substituted or unsubstituted propene.
  • Embodiment 14 The method of one of embodiments 7, 11, and 12, wherein the dehydrogenated polymer, the one or more olefin metathesis reagent(s), and the one or more isomerization reagent(s) are mixed simultaneously.
  • Embodiment 15. Embodiment 15.
  • Embodiment 16 The method of embodiment 15, wherein the dehydrogenated polymer and one or more additional olefin metathesis reagent(s) are mixed prior to adding the one or more olefin metathesis reagent(s) and the one or more isomerization reagent(s).
  • Embodiment 17 The method of one of embodiments 7, 11, and 12, wherein the one or more olefin metathesis reagent(s) comprises an ethenolysis catalyst.
  • Embodiment 18 The method of one of embodiments 7 and 11 to 17, wherein the one or more olefin metathesis reagent(s) comprises one or more homogeneous olefin metathesis catalyst(s) or one or more heterogeneous olefin metathesis catalyst(s).
  • Embodiment 19 The method of embodiment 18, wherein the one or more olefin metathesis reagent(s) further comprises ethylene.
  • Embodiment 20 The method of embodiment 18 or 19, wherein the homogeneous olefin metathesis catalyst is , , , or . . [0346] Embodiment 21.
  • Embodiment 22 The method of embodiment 18 or 19, wherein the homogeneous olefin metathesis catalyst is Re 2 O 7 /Al 2 O 3 or WO 3 /Al 2 O 3 .
  • Embodiment 23 The method of one of embodiments 7 and 11 to 21, wherein the one or more isomerization reagent(s) comprises one or more homogeneous isomerization catalyst(s) or one or more heterogeneous isomerization catalyst(s).
  • Embodiment 24 Embodiment 24.
  • Embodiment 25 The method of embodiment 23, wherein the one or more homogeneous isomerization catalyst(s) is .
  • Embodiment 26 The method of embodiment 23, wherein the one or more heterogeneous isomerization catalyst(s) is selected from: Na/Al 2 O 3 , K/Al 2 O 3 , Mg/Al 2 O 3 , MgO, NaO 2 , and KO 2 .
  • Embodiment 27 Embodiment 27.
  • Embodiment 28 The method of one of embodiments 7 to 27, wherein the one or more dehydrogenating reagent(s) comprises a transfer dehydrogenation catalyst.
  • Embodiment 29 The method of one of embodiments 7 to 28, wherein the one or more dehydrogenating reagent(s) comprises a hydrogen acceptor.
  • Embodiment 30 The method of one of embodiments 7 to 25, wherein the substituted or unsubstituted polymer is a high-density polyethylene, a low-density polyethylene, or a linear low-density polyethylene, or a co-polymer thereof.
  • Embodiment 33 The method of one of embodiments 7 to 32, wherein the one or more dehydrogenating reagent(s) comprises a heterogeneous dehydrogenating catalyst.
  • Embodiment 34 The method of embodiment 33, wherein the heterogeneous dehydrogenating catalyst comprises a plurality of metallic elements.
  • Embodiment 36 The method of one of embodiments 33 to 35, wherein the heterogeneous dehydrogenating catalyst is a Pt/Sn catalyst or a Pt/Zn catalyst.
  • Embodiment 37 The method of one of embodiments 33 to 36, wherein the heterogeneous dehydrogenating catalyst is Pt/Sn-Al2O3 or Pt/Zn-SiO2.
  • Embodiment 38 The method of one of embodiments 7 to 32, wherein the one or more dehydrogenating reagent(s) comprises a homogeneous dehydrogenating catalyst.
  • Embodiment 39 The method of embodiment 38, wherein the homogeneous dehydrogenating catalyst comprises an iridium catalyst, a rhodium catalyst, or a ruthenium catalyst.
  • Embodiment 40 The method of embodiment 38, wherein the homogeneous dehydrogenating catalyst comprises an iridium catalyst.
  • Embodiment 41 Embodiment 41.
  • the homogeneous dehydrogenating catalyst has the formula: ; wherein M is Ir, Rh, Ru, or Os; L 1 and L 2 are independently –O-, -S-, -NR 6 -, or substituted or unsubstituted alkylene; each R 3 and R 4 is independently substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; R 5 is independently halogen, -CX 5 3 , -CHX 5 2 , -CH 2 X 5 , -OCX 5 3 , -OCH 2 X 5 , -OCHX 5 2 , -CN, -SO n5 R 5D , -SO v5 NR 5
  • Embodiment 42 The method of embodiment 38, wherein the homogeneous dehydrogenating catalyst is .
  • Embodiment 43 The method of one of embodiments 7 to 42, wherein a percentage of from 1% to 3% of monomer units in the dehydrogenated polymer are unsaturated.
  • Embodiment 44 The method of one of embodiments 7 to 42, wherein a percentage of from 1.7% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated.
  • Embodiment 45 The method of one of embodiments 7 to 42, wherein a percentage of from 1.9% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated.
  • Embodiment 46 The method of embodiments 7 to 42, wherein a percentage of from 1.9% to 2.1% of monomer units in the dehydrogenated polymer are unsaturated.
  • Embodiment 47 The method of embodiment 46, wherein R 1 and R 2 are independently hydrogen, halogen, -CCl 3 , -CBr 3 , -CF 3 , -CI 3 , -CH 2 Cl, -CH 2 Br, -CH 2 F, -CH 2 I, -CHCl 2 , -CHBr 2 , -CHF 2 , -CHI2, -CN, -OH, -NH2, -COOH, -CONH2, -NO2, -SH, -SO3H, -OSO3H, -SO2NH2, ⁇ NHNH2, ⁇ ONH2, ⁇ NHC(O)NH2, -NHSO2H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl3, -OCBr3, -OCF3, -OCI3, -OCH2Cl, -OCH2Br, -OCH2F, -OCH2F,
  • Embodiment 48 The method of embodiment 46, wherein R 1 and R 2 are independently hydrogen or substituted or unsubstituted C1-C1000 alkyl.
  • Embodiment 49 The method of embodiment 46, wherein R 1 and R 2 are hydrogen.
  • Embodiment 50 The method of one of embodiments 1 to 49, conducted under continuous flow conditions.
  • Embodiment 51 A substituted or unsubstituted dehydrogenated polyethylene, wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are unsaturated.
  • Embodiment 52 A substituted or unsubstituted dehydrogenated polyethylene, wherein a percentage of from 0.01% to 1.5% or from 1.7% to 2.3% or from 2.4% to 4.3% or from 4.5% to 13.2% of monomer units are unsaturated.
  • Embodiment 53 A substituted or unsubstituted dehydrogenated polyethylene, having a number average molecular weight of 2,200 Da or greater.
  • Embodiment 54 The dehydrogenated polyethylene of embodiment 53, having a number average molecular weight of from 2,200 Da to 500,000 Da.
  • Embodiment 55 The dehydrogenated polyethylene of embodiment 53, having a number average molecular weight of from 2,200 Da to 6,500 Da or a number average molecular weight greater than 6,700 Da.
  • Embodiment 56 Embodiment 56.
  • Embodiment 57 The dehydrogenated polyethylene of one of embodiments 53 to 55, wherein a percentage of from 0.01% to 11% of monomer units are unsaturated.
  • Embodiment 58 The dehydrogenated polyethylene of one of embodiments 53 to 55, wherein a percentage of 8% or less of monomer units are unsaturated.
  • Embodiment 59 The dehydrogenated polyethylene of one of embodiments 53 to 55, wherein a percentage of from 1.5% to 3% of monomer units are unsaturated.
  • Embodiment 60 Embodiment 60.
  • Embodiment 61 The dehydrogenated polyethylene of one of embodiments 51 to 60, wherein the distribution of unsaturated monomer units is irregular.
  • Embodiment 62 Embodiment 62.
  • Embodiment 63 The dehydrogenated polyethylene of embodiment 62, wherein R 1 and R 2 are independently hydrogen, halogen, -CCl3, -CBr3, -CF3, -CI3, -CH2Cl, -CH2Br, -CH2F, -CH2I, -CHCl2, -CHBr2, -CHF2, -CHI 2 , -CN, -OH, -NH 2 , -COOH, -CONH 2 , -NO 2 , -SH, -SO 3 H, -OSO 3 H, -SO 2 NH 2 , ⁇ NHNH 2 , ⁇ ONH 2 , ⁇ NHC(O)NH 2 , -NHSO 2 H, -NHC(O)H, -NHC(O)OH, -NHOH, -OCCl 3 , -OCBr 3 , -OCF 3 , -OCI 3 , -OCH 2 Cl
  • Embodiment 64 The dehydrogenated polyethylene of embodiment 62, wherein R 1 and R 2 are independently hydrogen or substituted or unsubstituted C 1 -C 1000 alkyl.
  • Embodiment 65 The dehydrogenated polyethylene of embodiment 62, wherein R 1 and R 2 are hydrogen.
  • Example 1 Integrated catalysis for chemical recycling of polyethylene to propene [0391] Disclosed herein, inter alia, is the conversion of polyethylene to propene by integrating polyethylene dehydrogenation with tandem isomerizing ethenolysis of the resulting dehydro- polyethylene.
  • Polyolefins which account for 36% of global plastic production (1), are particularly durable and inert and are especially incompatible with traditional mechanical recycling. Only a small proportion of polyethylene (PE) waste is recovered by recycling (around 14% in 2015) (2), and the properties of the recycled materials are inferior to those of the virgin plastic. Polyolefins are prepared with molecular weights, molecular-weight distributions, and microstructures for specific applications. Thus, a mixture of polyethylenes that have been produced for diverse applications lack the properties of each individual component and possess accumulated additives and contaminants (2). Given the significant social, economic, and ecological threats from the accumulation of mixed polyolefin waste, new approaches to use this material as a carbon feedstock are needed (2-4).
  • dehydrogenation could be used to enable subsequent C-C bond cleavage by a combination of olefin metathesis and isomerization to form propene (FIG.1B) (19, 20).
  • FIG.1B olefin metathesis and isomerization to form propene
  • DIE dehydrogenation and isomerizing ethenolysis
  • HDPE High density polyethylene
  • Mn number average molecular weight
  • ⁇ polydispersity
  • HDPE (Item) refers to HDPE sourced from containers from commercial products, viz. a milk bottle and shampoo bottle.
  • LDPE (Commercial) refers to low-density polyethylene sourced from Sigma-Aldrich, with an M n of 35.1 kDa and polydispersity of 6.54.
  • LDPE (food packaging) refers to LDPE sourced from a commercial plastic bag used for food storage.
  • Pt/Sn/K- ⁇ Al 2 O 3 refers to a catalyst consisting of 0.5 wt % Pt, 1.2% Sn, and 6.8% K supported on gamma alumina.
  • the propene arising from dehydrogenated PE by the proposed scheme would consist entirely of the singly 13 C labeled isotopomer. This isotopic composition would be observed because scrambling would occur at the termini of propene by olefin metathesis during the IE but scrambling at the 2-position would not (FIG.3C). Accordingly, we subjected 13 C- labeled (99.9% 13 C) HDPE to DIE and characterized the resulting propene by mass spectrometry. The mass spectrum revealed an isotopic enrichment of the propene greater than 70%, demonstrating that the majority of propene observed from the DIE of PE results from polymer chain degradation. [0408] We also tested the potential to conduct DIE on samples of post-consumer PE.
  • Free energies for small molecules were approximated by the Joback method, while standard enthalpies of formation and molar entropies were sourced from the NIST chemistry webbook (36), and thermodynamic parameters for polyethylene were sourced from Broadhurst (37). in which nproducts and nreactants represent the stoichiometric coefficients of each product and reactant respectively, and ⁇ H f ° products and ⁇ H f ° products represent the enthalpy of formation for each product and reactant, and ⁇ H f ° rxn represents this parameter for the global reaction.
  • Example 3 Isomerizing ethenolysis of 1-octadecene with heterogeneous catalysts Catalyst Preparation [0417] This procedure was adapted from a procedure reported by Goldman and coworkers. See Goldman, A. S.; Roy, A. H.; Huang, Z.; Ahuja, R.; Schinski, W.; Brookhart, M. Science 312, 5771, 257-261 (2006). DOI: doi:10.1126/science.1123787 (stating: “In a vial, 1.20 g (4.47 mmol) of NH 4 ReO 4 was dissolved in 30 mL distilled water. This solution was added to 10 g (98 mmol) of ⁇ -Al2O3.
  • the suspension was swirled by hand for about a minute, then allowed to stand undisturbed at room temperature for 30 min. This cycle of swirling and standing was repeated until all of the water was absorbed by the alumina.
  • the solid was dried in a 120 °C oven overnight, then calcined at 550 °C for 3 hours under a flow of O 2 and cooled to room temperature under O2. The solid was brought into the drybox under vacuum to avoid exposure to moisture, and was stored under argon.”). This procedure produced Re2O7/ ⁇ -Al2O3 consisting of 8.4 wt% Re, or 0.45 mmol Re per gram of catalyst.
  • Na/ ⁇ -Al2O3 To a flame dried thick-walled Schlenk vessel were added sodium (160 mg, 6.96 mmol) and freshly calcined ⁇ -Al2O3 (1.840 g). The vessel was then sealed and heated to 150 °C for 12 h, resulting in the formation of a gray-blue solid. The mixture was then cooled, stored under inert atmosphere, and used in isomerizing ethenolysis experiments without further modification.

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