US3923836A - Chroman and chromene compounds - Google Patents

Chroman and chromene compounds Download PDF

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Publication number
US3923836A
US3923836A US380446A US38044673A US3923836A US 3923836 A US3923836 A US 3923836A US 380446 A US380446 A US 380446A US 38044673 A US38044673 A US 38044673A US 3923836 A US3923836 A US 3923836A
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US
United States
Prior art keywords
hydroxy
chromene
cyclohexyl
dimethyl
dimethylheptyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US380446A
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English (en)
Inventor
Paul E Bender
Bernard Loev
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SmithKline Beecham Corp
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SmithKline Corp
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Publication date
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Priority to US380446A priority Critical patent/US3923836A/en
Priority to BE146419A priority patent/BE817487A/xx
Priority to JP49081653A priority patent/JPS5040572A/ja
Priority to GB3155374A priority patent/GB1419919A/en
Priority to DE2434659A priority patent/DE2434659A1/de
Publication of USB380446I5 publication Critical patent/USB380446I5/en
Application granted granted Critical
Publication of US3923836A publication Critical patent/US3923836A/en
Assigned to SMITHKLINE BECKMAN CORPORATION reassignment SMITHKLINE BECKMAN CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE DATE: 03/04/82 Assignors: SMITHKLINE CORPORATION
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/64—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with oxygen atoms directly attached in position 8
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4

Definitions

  • R is lower alkyl
  • R is cycloalkyl or cycloalkenyl, said cycloalkyl and cycloalkenyl having 5-6 carbon atoms;
  • R is hydroxy or an alkali metal salt thereof, lower alkoxy or lower alkanoyloxy and R is a straight or branched alkyl or alkoxy group having 5 to 12 carbon atoms.
  • R is attached at the 5-position and R is attached at the 7- position.
  • Preferred compounds of this invention are represented by Formula I in which is a double bond, R is hydroxy attached at the 5-position and R is a straight or branched alkyl group having 5 to 12 carbon atoms which is attached at the 7-position. Also, preferably, R is cyclohexyl.
  • An advantageous compound of this invention is represented by Formula I in which is a double bond, R is methyl, R is cyclohexyl, R is hydroxy at the S-position and R is 1,2-dimethylheptyl at the 7-position, said compound being 4-cyclohexyl-7-( l,2-dimethylheptyl)- S-hydroxy-Z,2-dimethyl-2H chromene.
  • the compounds of Formula I are prepared by the fol- 2 0H 2 OH
  • R R and R are as defined above, R is lower alkyl and X is halogen.
  • a lower alkyl 3- R -3-oxopropionate is reacted with a R -substituteddihydroxybenzene compound in the presence of acid such as phosphorus oxychloride and sulfuric acid and the resulting hydroxycoumarin is reacted with a lower alkyl magnesium halide to give the hydroxychromenes of this invention.
  • a lower alkyl 3-R -3-oxopropionate is reacted with trihydroxybenzene to give a dihydroxycoumarin which is reacted with a lower alkyl magnesium halide to give a dihydroxychromene.
  • Alkylation by reacting the dihydroxychromene with an equimolar amount of an alkylating agent such as an alkyl halide in the presence of base gives chromene compounds of this invention in which R, is lower alkoxy.
  • the hydroxychromans of this invention are prepared by reducing the corresponding hydroxychromenes by catalytic hydrogenation using for example, palladium on carbon as the catalyst or by chemical reduction for example using sodium and ethanol.
  • the alkali metal salts of the hydroxychromenes and hydroxychromans are prepared by reacting the hydroxy compound with an alkali metal hydroxide, hydride or alkoxide.
  • the hydroxychromenes and hydroxychromans are esterified and etherified by standard procedures to give the compounds of this invention in which R is lower alkanoyl and lower alkyl.
  • R is lower alkanoyl
  • the compounds in which R, is lower alkanoyl are prepared by reacting the hydroxy compounds or alkali metal salts thereof with a lower alkanoyl halide or a lower alkanoic acid anhydride, preferably in the presence of a base.
  • the compounds in which R is lower alkyl are prepared, for example, by reacting an alkali metal derivative of a hydroxy compound with a lower alkyl halide.
  • the lower alkyl 3-R -3-oxopropionate starting materials are known to the art or are prepared by reacting R COO-( lower alkyl) with a lower alkyl acetate or by reacting R COCl with a lower alkyl acetoacetate by standard procedures.
  • R ,-substituted-dihydroxybenzene starting materials are either known to the art or are prepared by known procedures, as illustrated in examples herebelow.
  • the compounds of this invention have pharmacological activity such as central nervous system activity, for example the compounds have central nervous system depressant, sedative and tranquilizing activity.
  • the compounds may have analgesic, hypotensive, anti-inflammatory and diuretic activity.
  • the central nervous system activity is demonstrated by oral administration to rats at doses of about l0 mg./kg. to produce effects such as decreased spontaneous motor activity.
  • the compounds of the invention may'be combined with standard pharmaceutical carriers and administered internally in conventional dosage forms such as capsules, tablets or liquid preparations.
  • the compounds will be administered in an amount sufficient to produce the desired activity.
  • the pharmaceutical carrier may be for example a solid or a liquid.
  • solid carriers are lactose, magnesium stearate, terra alba, sucrose, talc, stearic acid, gelation, agar, pectin or acacia.
  • the amount of solid carrier will vary widely but preferably will be from about 25 mg. to about 1 gm.
  • Exemplary of liquid carriers ae syrup, peanut oil, olive oil. sesame oil, propylene glycol, polyethylene glycol (mol. wt. 200-400) and water.
  • the carrier or diluent may include a time delay material well known to the art such as. for example. glyceryl monostearate or glyceryl distearate alone or with a wax.
  • compositions can be employed.
  • the preparation may take the form of tablets. capsules. powders. suppositories. troches, lozenges, syrups. emulsions. sterile injectable liquids or liquid suspensions of solutions.
  • compositions are prepared by conventional techniques involving procedures such as mixing. granulating and compressing or dissolving the ingredients as appropriate to the desired preparation.
  • low alkyl and lower all oxy where used herein denote groups having 1-6, preferably 1-4, carbon atoms and lower alkanoyl” denotes groups having 2-6. preferably 2-4, carbon atoms.
  • the distillate in ethanol is refluxed with Raney nickel and redistilled.
  • the product is hydrogenated using 10 percent palladium/charcoal at 50 psi. for 30 minutes to give l,3-dimethoxy-5-( 1,1 ,2- trimethyloctyl)benzene.
  • the methoxy groups are demethylated by dissolving the 1,3-dimethoxy compound in a mixture of acetic acid and 48 percent hydrobromic acid, refluxing the mixture overnight, then pouring the mixture into ice-water, extracting with benzene, then concentrating and distilling to give 5-( 1,1 ,2- trimethyloctyl )resorcinol.
  • Example 1 In the procedure of Example 1 using 5-( 1,1,2-trimethyloctyllresorcinol in place of 5-( l,2-dimethylheptyl)- resorcinol, the product is 4-cyclohexyl-5-hydroxy-2,2- dimethyl- 7-( 1,1,2-trimethyloctyl )-2H-chromene.
  • EXAMPLE 5 A mixture of 3.0 g. of 4-cyclohexyl-7-(1,2-dimethylheptyl)-5-hydroxy-2,2-dimethyl-2H-chromene in 100 ml. of absolute ethanol and percent palladium on carbon is hydrogenated at 48 p.s.i. and C. for 1 hour. Chloroform (20 ml.) is added. The mixture is filtered and the solvent is removed from the filtrate. The resulting residue is distilled to give 4-cyclohexyl-7-( 1,2- dimethylheptyl)-5-hydroxy 2,Z-dimethylchroman.
  • EXAMPLE 6 A mixture of 55 g. of magnesium and 5 ml. of carbon tetrachloride is heated gently, then 200 ml. of methanol is added, followed by a solution of 285 g. of ethyl acetoacetate is 1,250 ml. of methanol and 1,500 ml. of tetrahydrofuran. The mixture is refluxed for five hours to dissolve the magnesium, and the solvent is evaporated in vacuo. The residue is dissolved in refluxing tetrahydrofuran and 270 g. of cyclopentanecarbonyl chloride is added over minutes. The mixture is refluxed for 1 hour, half of the solvent is distilled off at atmospheric pressure and the mixture is poured onto 5 kg.
  • EXAMPLE 7 A solution of 2.0 g. of 4-cyclohexyl-7-( 1 ,Z-dimethylheptyl)-5-hydroxy-2,Z-dimethyl-ZH-chromene in 40 ml. of acetic anhydride containing 1.0 g. of sodium acetate is heated at reflux for 5 hours. The excess anhydride is evaporated in vacuo and the residue is dissolved in water and extracted with ether. The extract is washed with water until neutral, then dried, evaporated and chromatographed and distilled to give 5-acetoxy-4- cyclohexyl-7-( l ,Z-dimethylheptyl)-2,2-dimethyl-2H- v chromene.
  • the product is 4-cyclohexyl- 7-( l,2-dimethylheptyl)-2.2-dimethyl-5-propionyloxy- 2H-chromene.
  • EXAMPLE 9 To 21 g. (0.1 mole) of finely powdered phosphorus pentachloride is added 15.4 g. (0.1 mole) of l-carbethoxy-cyclohex-Z-ene with stirring. After stirring the mixture at -100C. for 3 days, the phosphorus oxychloride is removed by distillation in vacuo. The residue is heated at 95C. with 5 mg. of palladium black until the evoluation of ethyl chloride ceases. Distillation in vacuo gives 2-cyclohexene-l-carbonyl chloride.
  • the product is 4-(2-cyclopentenyl)-5-hydroxy-2,2-dimethyl-7-( 1-methylheptyl)-2 H-chromene.
  • EXAMPLE 10 Sodium (1.84 g., 0.08 mole) is added over 30 minutes to 3.0 g. (0.008 mole) of 4-cyclopentyl-7-(l,2- dimethylheptyl)-5-hydroxy-2,Z-dimethyl-ZH-chromene in ml. of ethanol. The solution is cooled and 10ml. of water is added. The solution is then neutralized with dilute hydrochloric acid and the resulting mixture is evaporated to dryness in vacuo. The residue is extracted with water, dried and distilled to give 4- 7 cyclopentyl-7( 1,2-dimethylheptyl )--hydroxy-2.2- dimethylchroman.
  • EXAMPLE 1 1 By the procedure of Example 1. using ethyl magnesium bromide in place of methyl magnesium bromide. the product is 4-cyclohexy1-7-( l,2-dimethylheptyl)-5- hydroxy-Z.Z-diethyl-ZH-chromene.
  • EXAMPLE 12 4-.Cyclohexyl-7-( 1,Z-dimethylheptyl)-5-hydroxy-2.2- dimethyl-2H-chromene (2.0 g.) is refluxed with methanolic sodium hydroxide for one hour and the solution is then evaporated to give the sodium salt of 4-cyclohexyl-7-( 1,Z-dimethylheptyl)-5-hydroxy-2,Z-dimethyl-Zl-I- chromene.
  • EXAMPLE 13 Using 5-(1-ethylheptyl)resorcinol [prepared by reacting 3.5-dimethoxybenzamide with ethyl magnesium bromide, reacting the resulting 3.5-dimethoxyphenyl ethyl ketone with n-hexyl magnesium bromide, dehydrating and reducing the resulting 1,3-dimethoxy-5-( 1- hydroxy-1-ethy1hepty1)benzene and demethylating the methoxy groups of the resulting 1,3-dimethoxy-5-(1- ethy1hepty1)ben2ene] in place of 5-(1,2-dimethy1hepty1)resorcinol in the procedure of Example 1 gives 4- cyclohexyl-7-( 1-ethylheptyl)-5-hydroxy-2,2'dimethy1- ZH-chromene.
  • EXAMPLE 14 To a stirred solution of 126 g. (1.0 mole) of ph1oroglucinol and 19.0 g. (0.34 mole) of potassium hydroxide in dimethylformamide is added 186 g. (1.04 mole) of Z-bromoheptane. After heating the mixture for 16 hours at 100C. 250 ml. of acetic acid is added and the mixture is filtered. The filtrate is concentrated. dissolved in ether. washed with water and extracted with 10 percent aqueous sodium hydroxide solution. The alkaline solution is washed with ether. acidified with dilute hydrochloric acid and extracted with ether.
  • R is lower alkyl
  • R is cycloalkyl or cycloalkenyl, said cycloalkyl and cycloalkenyl having 5-6 carbon atoms;
  • R is hydroxy or an alkali metal salt thereof. lower alkoxy or lower alkanoyloxy and R is a straight or branched alkyl or alkoxy group having 5 to 12 carbon atoms.
  • a compound of claim 1 said compound being 4- cyclohexyl-7-( LZ-dimethylheptyl )-5-hydroxy-2,2- dimethyl-ZH-chromene.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
US380446A 1973-07-18 1973-07-18 Chroman and chromene compounds Expired - Lifetime US3923836A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US380446A US3923836A (en) 1973-07-18 1973-07-18 Chroman and chromene compounds
BE146419A BE817487A (fr) 1973-07-18 1974-07-10 Composes de chromane et de chromene
JP49081653A JPS5040572A (enrdf_load_stackoverflow) 1973-07-18 1974-07-15
GB3155374A GB1419919A (en) 1973-07-18 1974-07-17 Chroman and chromene compounds
DE2434659A DE2434659A1 (de) 1973-07-18 1974-07-18 Chroman- und chromenverbindungen, ihre salze, verfahren zu ihrer herstellung und arzneimittel

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US380446A US3923836A (en) 1973-07-18 1973-07-18 Chroman and chromene compounds

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USB380446I5 USB380446I5 (enrdf_load_stackoverflow) 1975-01-28
US3923836A true US3923836A (en) 1975-12-02

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JP (1) JPS5040572A (enrdf_load_stackoverflow)
BE (1) BE817487A (enrdf_load_stackoverflow)
DE (1) DE2434659A1 (enrdf_load_stackoverflow)
GB (1) GB1419919A (enrdf_load_stackoverflow)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4110347A (en) * 1974-05-31 1978-08-29 Beecham Group Limited Chroman derivatives
US4138401A (en) * 1976-03-29 1979-02-06 The United States Of America As Represented By The Secretary Of The Navy [3,2-g] Pyranoquinoline derivatives
US4296039A (en) * 1977-11-17 1981-10-20 Fidia S.P.A. Selected process for producing monohalogenated derivatives of 7-hydroxy-coumarin
US4788298A (en) * 1985-01-22 1988-11-29 Eastman Kodak Company Process for the preparation of coumarin compounds
US20140288230A1 (en) * 2011-10-19 2014-09-25 Bioformix Inc. Methylene beta-ketoester monomers, methods for making methylene beta-ketoester monomers, polymerizable compositions and products formed therefrom
US9518001B1 (en) 2016-05-13 2016-12-13 Sirrus, Inc. High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation
US9522381B2 (en) 2013-01-11 2016-12-20 Sirrus, Inc. Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway
US9523008B2 (en) 2012-03-30 2016-12-20 Sirrus, Inc. Ink coating formulations and polymerizable systems for producing the same
US9567475B1 (en) 2016-06-03 2017-02-14 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9617354B2 (en) 2015-06-01 2017-04-11 Sirrus, Inc. Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound
US9617377B1 (en) 2016-06-03 2017-04-11 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9637564B2 (en) 2014-09-08 2017-05-02 Sirrus, Inc. Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions
US9676875B2 (en) 2014-09-08 2017-06-13 Sirrus, Inc. Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions
US9683147B2 (en) 2015-05-29 2017-06-20 Sirrus, Inc. Encapsulated polymerization initiators, polymerization systems and methods using the same
US9752059B2 (en) 2012-11-16 2017-09-05 Sirrus, Inc. Plastics bonding systems and methods
US9790295B2 (en) 2014-09-08 2017-10-17 Sirrus, Inc. Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US9828324B2 (en) 2010-10-20 2017-11-28 Sirrus, Inc. Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom
US9938223B2 (en) 2015-02-04 2018-04-10 Sirrus, Inc. Catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US10047192B2 (en) 2012-06-01 2018-08-14 Sirrus, Inc. Optical material and articles formed therefrom
US10196481B2 (en) 2016-06-03 2019-02-05 Sirrus, Inc. Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof
US10414839B2 (en) 2010-10-20 2019-09-17 Sirrus, Inc. Polymers including a methylene beta-ketoester and products formed therefrom
US10428177B2 (en) 2016-06-03 2019-10-01 Sirrus, Inc. Water absorbing or water soluble polymers, intermediate compounds, and methods thereof
US10501400B2 (en) 2015-02-04 2019-12-10 Sirrus, Inc. Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US10607910B2 (en) 2012-11-30 2020-03-31 Sirrus, Inc. Composite compositions for electronics applications
US10913875B2 (en) 2012-03-30 2021-02-09 Sirrus, Inc. Composite and laminate articles and polymerizable systems for producing the same
WO2024148193A1 (en) * 2023-01-05 2024-07-11 Salk Institute For Biological Studies Synthetic analogs of cannabinol (cbn) for the treatment of age-related neurological disorders

Citations (1)

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Publication number Priority date Publication date Assignee Title
US3636058A (en) * 1966-03-25 1972-01-18 Hoffmann La Roche 7 10 - dihydro - 3 - alkyl - 6h - dibenzo(b d) pyran-6 9(8h)-diones and 5-hydroxy-7-alkyl-4-chromanones

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3636058A (en) * 1966-03-25 1972-01-18 Hoffmann La Roche 7 10 - dihydro - 3 - alkyl - 6h - dibenzo(b d) pyran-6 9(8h)-diones and 5-hydroxy-7-alkyl-4-chromanones

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4110347A (en) * 1974-05-31 1978-08-29 Beecham Group Limited Chroman derivatives
US4138401A (en) * 1976-03-29 1979-02-06 The United States Of America As Represented By The Secretary Of The Navy [3,2-g] Pyranoquinoline derivatives
US4296039A (en) * 1977-11-17 1981-10-20 Fidia S.P.A. Selected process for producing monohalogenated derivatives of 7-hydroxy-coumarin
US4788298A (en) * 1985-01-22 1988-11-29 Eastman Kodak Company Process for the preparation of coumarin compounds
US10414839B2 (en) 2010-10-20 2019-09-17 Sirrus, Inc. Polymers including a methylene beta-ketoester and products formed therefrom
US9828324B2 (en) 2010-10-20 2017-11-28 Sirrus, Inc. Methylene beta-diketone monomers, methods for making methylene beta-diketone monomers, polymerizable compositions and products formed therefrom
US9969822B2 (en) 2011-10-19 2018-05-15 Sirrus, Inc. Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom
US9512058B2 (en) 2011-10-19 2016-12-06 Sirrus Inc. Multifunctional monomers, methods for making multifunctional monomers, polymerizable compostions and products formed thereform
US9527795B2 (en) * 2011-10-19 2016-12-27 Sirrus, Inc. Methylene beta-ketoester monomers, methods for making methylene beta-ketoester monomers, polymerizable compositions and products formed therefrom
US20140288230A1 (en) * 2011-10-19 2014-09-25 Bioformix Inc. Methylene beta-ketoester monomers, methods for making methylene beta-ketoester monomers, polymerizable compositions and products formed therefrom
US10611861B2 (en) 2011-10-19 2020-04-07 Sirrus, Inc. Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed thereform
US10604601B2 (en) 2011-10-19 2020-03-31 Sirrus, Inc. Multifunctional monomers, methods for making multifunctional monomers, polymerizable compositions and products formed therefrom
US9523008B2 (en) 2012-03-30 2016-12-20 Sirrus, Inc. Ink coating formulations and polymerizable systems for producing the same
US10913875B2 (en) 2012-03-30 2021-02-09 Sirrus, Inc. Composite and laminate articles and polymerizable systems for producing the same
US10047192B2 (en) 2012-06-01 2018-08-14 Sirrus, Inc. Optical material and articles formed therefrom
US9752059B2 (en) 2012-11-16 2017-09-05 Sirrus, Inc. Plastics bonding systems and methods
US10607910B2 (en) 2012-11-30 2020-03-31 Sirrus, Inc. Composite compositions for electronics applications
US10086355B2 (en) 2013-01-11 2018-10-02 Sirrus, Inc. Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway
US9522381B2 (en) 2013-01-11 2016-12-20 Sirrus, Inc. Method to obtain methylene malonate via bis(hydroxymethyl) malonate pathway
US9676875B2 (en) 2014-09-08 2017-06-13 Sirrus, Inc. Solution polymers including one or more 1,1-disubstituted alkene compounds, solution polymerization methods, and polymer compositions
US10081685B2 (en) 2014-09-08 2018-09-25 Sirrus, Inc. Emulson polymers including one or more 1,1-disubstituted alkene compounds, emulson methods, and polymer compositions
US9890227B1 (en) 2014-09-08 2018-02-13 Sirrus, Inc. Compositions containing 1,1-di-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US10308802B2 (en) 2014-09-08 2019-06-04 Sirrus, Inc. Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof
US9969819B2 (en) 2014-09-08 2018-05-15 Sirrus, Inc. Pressure sensitive adhesive including a 1,1-disubstituted alkene compound
US10184073B2 (en) 2014-09-08 2019-01-22 Sirrus, Inc. Emulsion including polymers containing a 1,1-disubstituted alkene compound, adhesives, coatings, and methods thereof
US9637564B2 (en) 2014-09-08 2017-05-02 Sirrus, Inc. Emulsion polymers including one or more 1,1-disubstituted alkene compounds, emulsion methods, and polymer compositions
US9790295B2 (en) 2014-09-08 2017-10-17 Sirrus, Inc. Compositions containing 1,1-disubstituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US10167348B2 (en) 2014-09-08 2019-01-01 Sirrus, Inc. Solution polymers formed from methylene malonate monomers, polymerization, and solution polymer products
US10633566B2 (en) 2014-09-08 2020-04-28 Sirrus, Inc. Polymers containing a 1,1-disubstituted alkene compound
US11021617B2 (en) 2014-09-08 2021-06-01 Sirrus, Inc. Polymers including one or more 1,1-disubstituted alkene compounds and polymer compositions thereof
US10519257B2 (en) 2014-09-08 2019-12-31 Sirrus, Inc. Compositions containing 1,1-di-carbonyl-substituted alkene compounds for preparing polymers having enhanced glass transition temperatures
US10501400B2 (en) 2015-02-04 2019-12-10 Sirrus, Inc. Heterogeneous catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US9938223B2 (en) 2015-02-04 2018-04-10 Sirrus, Inc. Catalytic transesterification of ester compounds with groups reactive under transesterification conditions
US10087272B2 (en) 2015-05-29 2018-10-02 Sirrus, Inc. Encapsulated polymerization initiators, polymerization systems and methods using the same
US9683147B2 (en) 2015-05-29 2017-06-20 Sirrus, Inc. Encapsulated polymerization initiators, polymerization systems and methods using the same
US9617354B2 (en) 2015-06-01 2017-04-11 Sirrus, Inc. Electroinitiated polymerization of compositions having a 1,1-disubstituted alkene compound
US9518001B1 (en) 2016-05-13 2016-12-13 Sirrus, Inc. High purity 1,1-dicarbonyl substituted-1-alkenes and methods for their preparation
US10428177B2 (en) 2016-06-03 2019-10-01 Sirrus, Inc. Water absorbing or water soluble polymers, intermediate compounds, and methods thereof
US10196481B2 (en) 2016-06-03 2019-02-05 Sirrus, Inc. Polymer and other compounds functionalized with terminal 1,1-disubstituted alkene monomer(s) and methods thereof
US10150886B2 (en) 2016-06-03 2018-12-11 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US10087283B2 (en) 2016-06-03 2018-10-02 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9745413B1 (en) 2016-06-03 2017-08-29 Sirrus, Inc. Polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
US9718989B1 (en) 2016-06-03 2017-08-01 Sirrus, Inc. Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes
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USB380446I5 (enrdf_load_stackoverflow) 1975-01-28
BE817487A (fr) 1975-01-10

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