Patent
US 9,273,023MODULAR SYNTHESIS OF GRAPHENE NANORIBBONS AND GRAPHENE SUBSTRUCTURES FROM OLIGO-ALKYNES
Igor Alabugin
US
Copyright © 2026 Matter42. All rights reserved.
Patent
Atlas literature
Patent
US 9,273,023Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a depiction of prior art syntheses of graphene. [0015]
FIG. 2. Because intermolecular activation does not proceed with the sufficient selectivity for the substrates with more than three alkynes, the method of the …
FIG. 3) by employing ethynyltrimethylsilane as the R group and deprotecting the compound via base- mediated (for example,potassium carbonate or …
FIG. 4, the oligo-alkyne compound comprises four alkyne moieties. A general structure of an oligo-alkyne compound comprising four alkyne moieties is shown in …
FIG. 5. Scheme 2 depicts cascade cyclization of substituted enediynes and Potential Energy surface (PES) for the transformation of SVG …
FIG. 6), prior to cycliziation. Xanthates can be selectively activated in the presence of alkyne using either light or lauroyl peroxide/thermal initiation. …
FIG. 7 depicts Scheme 4, which is a sequence of reactions for the synthesis of o- aryleneethynylene tetramer, the mechanism of cascade cyclization, and the …
FIG. 8. Starting with a monoalkyne "linchpin" (or any other core molecule with an odd number of alkynes) provides symmetric molecules with an odd number of …
FIG. 9. However, all oligo-alkynes, independent on having an odd or an even number of the triple bonds, can be fully converted to a polyaromatic molecules as …
FIGS. 10 and 11. In some embodiments, wider ribbons are possible by cyclizing oligo-alkynes having the general structure (X): SVG …
FIG. 12E, including the conditions for cyclization of the assembled compound. [0087] In some embodiments, the present invention is directed to the cyclization …
FIG. 13. DETAILED DESCRIPTION OF THE EMBODIMENT(S) OF THE INVENTION [0029] The present invention is directed to the synthesis of conjugated, cyclized …
FIGS. 14, 15, and 16, respectively. [0093] In any of the oligo-alkyne structures according to the present invention, modular assembly allows the linkage of any …
FIGS. 15 A through 15C depict the synthetic scheme for the preparation of oligo-alkyne of compound B of
FIGS. 16 A through 16C depict the synthetic scheme for the preparation of oligo-alkyne of compound C of
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of cyclizing a compound preparing a multicyclic structure, the method comprising: cyclizing a contacting the compound with Bu 3 SnH, wherein the compound comprises comprising repeat units having the following structure (I): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.1.svg 2 3.67 Black and white wherein: n is an integer having a value of at least three and less than 25; Rai, Ra 2, Ra 3, and Ra 4 are each independently carbon or nitrogen; and R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aliphatic moiety, and a substituted or unsubstituted alkoxy; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; or, alternatively, R A I, R A2, R A3, and R A₄ are each carbon; R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted aliphatic moiety; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; and any two Page 2 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT adjacent R A l, R A 2, R A3, and R A₄ and the R 1, R 2, R 3, and R 4, respectively bonded thereto together with the atoms to which they are bonded complete naphthalene or anthracene; T 1 and T₂ are each independently selected from the group consisting of hydrogen, an aliphatic moiety having from 1 to 18 carbon atoms; an aromatic moiety having from three to 18 carbon atoms; an alkoxy moiety having from 1 to 6 carbon atoms; and a cyan o moiety; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.2.svg 1.48 2.47 Black and white wherein: Y is selected from the group consisting of bromine, iodine, and xanthyl, and a carbonyl compound which can be converted into a radical; and Z is selected from the group consisting of O, S, S(O), SO 2, CH 2, and NCH 3.
The method of claim 1 wherein n has a value between four and 25.
The method of claim 1 wherein the compound has the following structure (III): Page 3 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.3.svg 2 3.45 Black and white wherein n has a value between four and 25; R 1, R 2, R 3, R 4, Ti, and T₂ are as defined in claim 1; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.4.svg 1.48 2.47 Black and white wherein Y and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (VIII): Page 4 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.5.svg 3.89 3.76 Black and white Structure (VIII) wherein R 1, R 2, R 3, R 4, T1, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (IX): Page 7 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.10.svg 5.94 4.69 Black and white wherein R 1, R 2, R 3, R 4, Ti, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (Xa): Page 8 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.11.svg 5.34 4.44 Black and white wherein R 2, R 3, Y, and Z are as defined above in connection with claim 1.
canceled
canceled
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material1 process step
Synthesis of model enediynes: illustrates the general technique for synthesizing the model compound and for the addition of aromatic-alkyne building blocks.
1 process step
Optimization of Cascade Initiation: reaction sequences performed to optimize the initiation of the cyclization reaction.
No measurements recorded
Mechanism of Cascade Initiation: reaction sequence demonstrating the mechanism of cascade initiation of the cyclization reaction.
No measurements recorded
General Procedure for Synthesis of Compounds: describes general laboratory procedures including solvents (THF and hexanes dried over sodium), column chromatography on silica gel (60 Å), NMR conditions (1H at 400/600 MHz, 13C at 100/150 MHz in CDCl₃ and CD₃CN).
2 materials1 process step
General Procedure for protection of 2,3-iodophenol with 'weak link' group (a): suspension of 2,3-iodophenol (0.77 mmol), K₂CO₃ (1.69 mmol), and 18-crown-6 (0.04 mmol) in acetone refluxed; 1,2-dibromoethane (3.06 mmol) added dropwise; purified by flash chromatography to afford compound a.
2 materials1 process step
Procedure for synthesis of 3-iodophenyl diethylcarbamate (b): 3-iodophenol treated with NaH in THF, then N,N-diethylcarbamoyl chloride added; purified by column chromatography to afford compound b.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenyl diethylcarbamate (c): LDA generated from n-BuLi and i-Pr₂NH in THF at 0°C, cooled to -78°C, compound added, then iodine in THF added; workup and column chromatography to afford compound c.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenol (d): carbamate 3 in EtOH treated with excess NaOH under reflux for 5-8 h; workup and column chromatography to afford compound d.
2 materials1 process step
General Procedure for Sonogashira cross coupling of 6 with different substituted acetylenes (1): aryl dihalide (0.59 mmol), PdCl₂(PPh₃)2 (29.70 µmol), CuI (29.70 µmol) in triethylamine; 4-ethynyl-anisole (1.49 mmol, 2.5 equiv.) added; 8 h reaction; purified by flash chromatography to afford compound 1.
2 materials1 process step
General Procedure for radical cascade of (2): bis-methylbenzene (1) (40.00 mg) in benzene, Bu₃SnH (59.70 mg) in benzene, and AIBN (1.53 mg) in benzene; nitrogen degassed; Bu₃SnH and AIBN added by syringe pump over 6 h to refluxing solution; purified by preparatory TLC to afford compound 2.
1 material1 process step
General Procedure for Finkelstein reaction of (3) and (13): sodium iodide added to compound (1c) (55 mg, 0.13 mmol) in acetone, heated to 50°C under nitrogen for 8 h.
Materials described outside the worked examples.
oligo-alkyne compound comprising repeat units of structure (I)
graphene substructures/multicyclic polyaromatic products
Patent
Atlas literature
Patent
US 9,273,023Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a depiction of prior art syntheses of graphene. [0015]
FIG. 2. Because intermolecular activation does not proceed with the sufficient selectivity for the substrates with more than three alkynes, the method of the …
FIG. 3) by employing ethynyltrimethylsilane as the R group and deprotecting the compound via base- mediated (for example,potassium carbonate or …
FIG. 4, the oligo-alkyne compound comprises four alkyne moieties. A general structure of an oligo-alkyne compound comprising four alkyne moieties is shown in …
FIG. 5. Scheme 2 depicts cascade cyclization of substituted enediynes and Potential Energy surface (PES) for the transformation of SVG …
FIG. 6), prior to cycliziation. Xanthates can be selectively activated in the presence of alkyne using either light or lauroyl peroxide/thermal initiation. …
FIG. 7 depicts Scheme 4, which is a sequence of reactions for the synthesis of o- aryleneethynylene tetramer, the mechanism of cascade cyclization, and the …
FIG. 8. Starting with a monoalkyne "linchpin" (or any other core molecule with an odd number of alkynes) provides symmetric molecules with an odd number of …
FIG. 9. However, all oligo-alkynes, independent on having an odd or an even number of the triple bonds, can be fully converted to a polyaromatic molecules as …
FIGS. 10 and 11. In some embodiments, wider ribbons are possible by cyclizing oligo-alkynes having the general structure (X): SVG …
FIG. 12E, including the conditions for cyclization of the assembled compound. [0087] In some embodiments, the present invention is directed to the cyclization …
FIG. 13. DETAILED DESCRIPTION OF THE EMBODIMENT(S) OF THE INVENTION [0029] The present invention is directed to the synthesis of conjugated, cyclized …
FIGS. 14, 15, and 16, respectively. [0093] In any of the oligo-alkyne structures according to the present invention, modular assembly allows the linkage of any …
FIGS. 15 A through 15C depict the synthetic scheme for the preparation of oligo-alkyne of compound B of
FIGS. 16 A through 16C depict the synthetic scheme for the preparation of oligo-alkyne of compound C of
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of cyclizing a compound preparing a multicyclic structure, the method comprising: cyclizing a contacting the compound with Bu 3 SnH, wherein the compound comprises comprising repeat units having the following structure (I): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.1.svg 2 3.67 Black and white wherein: n is an integer having a value of at least three and less than 25; Rai, Ra 2, Ra 3, and Ra 4 are each independently carbon or nitrogen; and R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aliphatic moiety, and a substituted or unsubstituted alkoxy; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; or, alternatively, R A I, R A2, R A3, and R A₄ are each carbon; R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted aliphatic moiety; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; and any two Page 2 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT adjacent R A l, R A 2, R A3, and R A₄ and the R 1, R 2, R 3, and R 4, respectively bonded thereto together with the atoms to which they are bonded complete naphthalene or anthracene; T 1 and T₂ are each independently selected from the group consisting of hydrogen, an aliphatic moiety having from 1 to 18 carbon atoms; an aromatic moiety having from three to 18 carbon atoms; an alkoxy moiety having from 1 to 6 carbon atoms; and a cyan o moiety; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.2.svg 1.48 2.47 Black and white wherein: Y is selected from the group consisting of bromine, iodine, and xanthyl, and a carbonyl compound which can be converted into a radical; and Z is selected from the group consisting of O, S, S(O), SO 2, CH 2, and NCH 3.
The method of claim 1 wherein n has a value between four and 25.
The method of claim 1 wherein the compound has the following structure (III): Page 3 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.3.svg 2 3.45 Black and white wherein n has a value between four and 25; R 1, R 2, R 3, R 4, Ti, and T₂ are as defined in claim 1; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.4.svg 1.48 2.47 Black and white wherein Y and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (VIII): Page 4 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.5.svg 3.89 3.76 Black and white Structure (VIII) wherein R 1, R 2, R 3, R 4, T1, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (IX): Page 7 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.10.svg 5.94 4.69 Black and white wherein R 1, R 2, R 3, R 4, Ti, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (Xa): Page 8 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.11.svg 5.34 4.44 Black and white wherein R 2, R 3, Y, and Z are as defined above in connection with claim 1.
canceled
canceled
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material1 process step
Synthesis of model enediynes: illustrates the general technique for synthesizing the model compound and for the addition of aromatic-alkyne building blocks.
1 process step
Optimization of Cascade Initiation: reaction sequences performed to optimize the initiation of the cyclization reaction.
No measurements recorded
Mechanism of Cascade Initiation: reaction sequence demonstrating the mechanism of cascade initiation of the cyclization reaction.
No measurements recorded
General Procedure for Synthesis of Compounds: describes general laboratory procedures including solvents (THF and hexanes dried over sodium), column chromatography on silica gel (60 Å), NMR conditions (1H at 400/600 MHz, 13C at 100/150 MHz in CDCl₃ and CD₃CN).
2 materials1 process step
General Procedure for protection of 2,3-iodophenol with 'weak link' group (a): suspension of 2,3-iodophenol (0.77 mmol), K₂CO₃ (1.69 mmol), and 18-crown-6 (0.04 mmol) in acetone refluxed; 1,2-dibromoethane (3.06 mmol) added dropwise; purified by flash chromatography to afford compound a.
2 materials1 process step
Procedure for synthesis of 3-iodophenyl diethylcarbamate (b): 3-iodophenol treated with NaH in THF, then N,N-diethylcarbamoyl chloride added; purified by column chromatography to afford compound b.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenyl diethylcarbamate (c): LDA generated from n-BuLi and i-Pr₂NH in THF at 0°C, cooled to -78°C, compound added, then iodine in THF added; workup and column chromatography to afford compound c.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenol (d): carbamate 3 in EtOH treated with excess NaOH under reflux for 5-8 h; workup and column chromatography to afford compound d.
2 materials1 process step
General Procedure for Sonogashira cross coupling of 6 with different substituted acetylenes (1): aryl dihalide (0.59 mmol), PdCl₂(PPh₃)2 (29.70 µmol), CuI (29.70 µmol) in triethylamine; 4-ethynyl-anisole (1.49 mmol, 2.5 equiv.) added; 8 h reaction; purified by flash chromatography to afford compound 1.
2 materials1 process step
General Procedure for radical cascade of (2): bis-methylbenzene (1) (40.00 mg) in benzene, Bu₃SnH (59.70 mg) in benzene, and AIBN (1.53 mg) in benzene; nitrogen degassed; Bu₃SnH and AIBN added by syringe pump over 6 h to refluxing solution; purified by preparatory TLC to afford compound 2.
1 material1 process step
General Procedure for Finkelstein reaction of (3) and (13): sodium iodide added to compound (1c) (55 mg, 0.13 mmol) in acetone, heated to 50°C under nitrogen for 8 h.
Materials described outside the worked examples.
oligo-alkyne compound comprising repeat units of structure (I)
graphene substructures/multicyclic polyaromatic products
Patent
Atlas literature
Patent
US 9,273,023Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a depiction of prior art syntheses of graphene. [0015]
FIG. 2. Because intermolecular activation does not proceed with the sufficient selectivity for the substrates with more than three alkynes, the method of the …
FIG. 3) by employing ethynyltrimethylsilane as the R group and deprotecting the compound via base- mediated (for example,potassium carbonate or …
FIG. 4, the oligo-alkyne compound comprises four alkyne moieties. A general structure of an oligo-alkyne compound comprising four alkyne moieties is shown in …
FIG. 5. Scheme 2 depicts cascade cyclization of substituted enediynes and Potential Energy surface (PES) for the transformation of SVG …
FIG. 6), prior to cycliziation. Xanthates can be selectively activated in the presence of alkyne using either light or lauroyl peroxide/thermal initiation. …
FIG. 7 depicts Scheme 4, which is a sequence of reactions for the synthesis of o- aryleneethynylene tetramer, the mechanism of cascade cyclization, and the …
FIG. 8. Starting with a monoalkyne "linchpin" (or any other core molecule with an odd number of alkynes) provides symmetric molecules with an odd number of …
FIG. 9. However, all oligo-alkynes, independent on having an odd or an even number of the triple bonds, can be fully converted to a polyaromatic molecules as …
FIGS. 10 and 11. In some embodiments, wider ribbons are possible by cyclizing oligo-alkynes having the general structure (X): SVG …
FIG. 12E, including the conditions for cyclization of the assembled compound. [0087] In some embodiments, the present invention is directed to the cyclization …
FIG. 13. DETAILED DESCRIPTION OF THE EMBODIMENT(S) OF THE INVENTION [0029] The present invention is directed to the synthesis of conjugated, cyclized …
FIGS. 14, 15, and 16, respectively. [0093] In any of the oligo-alkyne structures according to the present invention, modular assembly allows the linkage of any …
FIGS. 15 A through 15C depict the synthetic scheme for the preparation of oligo-alkyne of compound B of
FIGS. 16 A through 16C depict the synthetic scheme for the preparation of oligo-alkyne of compound C of
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of cyclizing a compound preparing a multicyclic structure, the method comprising: cyclizing a contacting the compound with Bu 3 SnH, wherein the compound comprises comprising repeat units having the following structure (I): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.1.svg 2 3.67 Black and white wherein: n is an integer having a value of at least three and less than 25; Rai, Ra 2, Ra 3, and Ra 4 are each independently carbon or nitrogen; and R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aliphatic moiety, and a substituted or unsubstituted alkoxy; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; or, alternatively, R A I, R A2, R A3, and R A₄ are each carbon; R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted aliphatic moiety; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; and any two Page 2 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT adjacent R A l, R A 2, R A3, and R A₄ and the R 1, R 2, R 3, and R 4, respectively bonded thereto together with the atoms to which they are bonded complete naphthalene or anthracene; T 1 and T₂ are each independently selected from the group consisting of hydrogen, an aliphatic moiety having from 1 to 18 carbon atoms; an aromatic moiety having from three to 18 carbon atoms; an alkoxy moiety having from 1 to 6 carbon atoms; and a cyan o moiety; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.2.svg 1.48 2.47 Black and white wherein: Y is selected from the group consisting of bromine, iodine, and xanthyl, and a carbonyl compound which can be converted into a radical; and Z is selected from the group consisting of O, S, S(O), SO 2, CH 2, and NCH 3.
The method of claim 1 wherein n has a value between four and 25.
The method of claim 1 wherein the compound has the following structure (III): Page 3 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.3.svg 2 3.45 Black and white wherein n has a value between four and 25; R 1, R 2, R 3, R 4, Ti, and T₂ are as defined in claim 1; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.4.svg 1.48 2.47 Black and white wherein Y and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (VIII): Page 4 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.5.svg 3.89 3.76 Black and white Structure (VIII) wherein R 1, R 2, R 3, R 4, T1, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (IX): Page 7 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.10.svg 5.94 4.69 Black and white wherein R 1, R 2, R 3, R 4, Ti, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (Xa): Page 8 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.11.svg 5.34 4.44 Black and white wherein R 2, R 3, Y, and Z are as defined above in connection with claim 1.
canceled
canceled
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material1 process step
Synthesis of model enediynes: illustrates the general technique for synthesizing the model compound and for the addition of aromatic-alkyne building blocks.
1 process step
Optimization of Cascade Initiation: reaction sequences performed to optimize the initiation of the cyclization reaction.
No measurements recorded
Mechanism of Cascade Initiation: reaction sequence demonstrating the mechanism of cascade initiation of the cyclization reaction.
No measurements recorded
General Procedure for Synthesis of Compounds: describes general laboratory procedures including solvents (THF and hexanes dried over sodium), column chromatography on silica gel (60 Å), NMR conditions (1H at 400/600 MHz, 13C at 100/150 MHz in CDCl₃ and CD₃CN).
2 materials1 process step
General Procedure for protection of 2,3-iodophenol with 'weak link' group (a): suspension of 2,3-iodophenol (0.77 mmol), K₂CO₃ (1.69 mmol), and 18-crown-6 (0.04 mmol) in acetone refluxed; 1,2-dibromoethane (3.06 mmol) added dropwise; purified by flash chromatography to afford compound a.
2 materials1 process step
Procedure for synthesis of 3-iodophenyl diethylcarbamate (b): 3-iodophenol treated with NaH in THF, then N,N-diethylcarbamoyl chloride added; purified by column chromatography to afford compound b.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenyl diethylcarbamate (c): LDA generated from n-BuLi and i-Pr₂NH in THF at 0°C, cooled to -78°C, compound added, then iodine in THF added; workup and column chromatography to afford compound c.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenol (d): carbamate 3 in EtOH treated with excess NaOH under reflux for 5-8 h; workup and column chromatography to afford compound d.
2 materials1 process step
General Procedure for Sonogashira cross coupling of 6 with different substituted acetylenes (1): aryl dihalide (0.59 mmol), PdCl₂(PPh₃)2 (29.70 µmol), CuI (29.70 µmol) in triethylamine; 4-ethynyl-anisole (1.49 mmol, 2.5 equiv.) added; 8 h reaction; purified by flash chromatography to afford compound 1.
2 materials1 process step
General Procedure for radical cascade of (2): bis-methylbenzene (1) (40.00 mg) in benzene, Bu₃SnH (59.70 mg) in benzene, and AIBN (1.53 mg) in benzene; nitrogen degassed; Bu₃SnH and AIBN added by syringe pump over 6 h to refluxing solution; purified by preparatory TLC to afford compound 2.
1 material1 process step
General Procedure for Finkelstein reaction of (3) and (13): sodium iodide added to compound (1c) (55 mg, 0.13 mmol) in acetone, heated to 50°C under nitrogen for 8 h.
Materials described outside the worked examples.
oligo-alkyne compound comprising repeat units of structure (I)
graphene substructures/multicyclic polyaromatic products
Patent
Atlas literature
Patent
US 9,273,023Patent drawings and their descriptions. Click a drawing to enlarge it.
FIG. 1 is a depiction of prior art syntheses of graphene. [0015]
FIG. 2. Because intermolecular activation does not proceed with the sufficient selectivity for the substrates with more than three alkynes, the method of the …
FIG. 3) by employing ethynyltrimethylsilane as the R group and deprotecting the compound via base- mediated (for example,potassium carbonate or …
FIG. 4, the oligo-alkyne compound comprises four alkyne moieties. A general structure of an oligo-alkyne compound comprising four alkyne moieties is shown in …
FIG. 5. Scheme 2 depicts cascade cyclization of substituted enediynes and Potential Energy surface (PES) for the transformation of SVG …
FIG. 6), prior to cycliziation. Xanthates can be selectively activated in the presence of alkyne using either light or lauroyl peroxide/thermal initiation. …
FIG. 7 depicts Scheme 4, which is a sequence of reactions for the synthesis of o- aryleneethynylene tetramer, the mechanism of cascade cyclization, and the …
FIG. 8. Starting with a monoalkyne "linchpin" (or any other core molecule with an odd number of alkynes) provides symmetric molecules with an odd number of …
FIG. 9. However, all oligo-alkynes, independent on having an odd or an even number of the triple bonds, can be fully converted to a polyaromatic molecules as …
FIGS. 10 and 11. In some embodiments, wider ribbons are possible by cyclizing oligo-alkynes having the general structure (X): SVG …
FIG. 12E, including the conditions for cyclization of the assembled compound. [0087] In some embodiments, the present invention is directed to the cyclization …
FIG. 13. DETAILED DESCRIPTION OF THE EMBODIMENT(S) OF THE INVENTION [0029] The present invention is directed to the synthesis of conjugated, cyclized …
FIGS. 14, 15, and 16, respectively. [0093] In any of the oligo-alkyne structures according to the present invention, modular assembly allows the linkage of any …
FIGS. 15 A through 15C depict the synthetic scheme for the preparation of oligo-alkyne of compound B of
FIGS. 16 A through 16C depict the synthetic scheme for the preparation of oligo-alkyne of compound C of
Claims define the patent's legal scope. Independent claims stand alone; dependent claims (nested) narrow them. Click a claim to expand its dependents.
A method of cyclizing a compound preparing a multicyclic structure, the method comprising: cyclizing a contacting the compound with Bu 3 SnH, wherein the compound comprises comprising repeat units having the following structure (I): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.1.svg 2 3.67 Black and white wherein: n is an integer having a value of at least three and less than 25; Rai, Ra 2, Ra 3, and Ra 4 are each independently carbon or nitrogen; and R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted aliphatic moiety, and a substituted or unsubstituted alkoxy; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; or, alternatively, R A I, R A2, R A3, and R A₄ are each carbon; R 1, R 2, R 3, and R 4 are each independently selected from the group consisting of hydrogen and a substituted or unsubstituted aliphatic moiety; wherein the substituents of substituted aliphatic moiety are selected from the group consisting of chlorine, bromine, amino, and cyan o; and any two Page 2 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT adjacent R A l, R A 2, R A3, and R A₄ and the R 1, R 2, R 3, and R 4, respectively bonded thereto together with the atoms to which they are bonded complete naphthalene or anthracene; T 1 and T₂ are each independently selected from the group consisting of hydrogen, an aliphatic moiety having from 1 to 18 carbon atoms; an aromatic moiety having from three to 18 carbon atoms; an alkoxy moiety having from 1 to 6 carbon atoms; and a cyan o moiety; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.2.svg 1.48 2.47 Black and white wherein: Y is selected from the group consisting of bromine, iodine, and xanthyl, and a carbonyl compound which can be converted into a radical; and Z is selected from the group consisting of O, S, S(O), SO 2, CH 2, and NCH 3.
The method of claim 1 wherein n has a value between four and 25.
The method of claim 1 wherein the compound has the following structure (III): Page 3 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.3.svg 2 3.45 Black and white wherein n has a value between four and 25; R 1, R 2, R 3, R 4, Ti, and T₂ are as defined in claim 1; and further wherein at least one of the repeat units comprises an R 1 moiety having the structure (II): SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.4.svg 1.48 2.47 Black and white wherein Y and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (VIII): Page 4 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.5.svg 3.89 3.76 Black and white Structure (VIII) wherein R 1, R 2, R 3, R 4, T1, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (IX): Page 7 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.10.svg 5.94 4.69 Black and white wherein R 1, R 2, R 3, R 4, Ti, T2, Y, and Z are as defined in claim 1.
The method of claim 1 wherein the compound has the following structure (Xa): Page 8 of 13 FSU 15- 082 ALABUGIN (31119-45) PATENT SVG 14541737.11-03-2015.IGJGQVM₈PXXIFW3.CLM.11.svg 5.34 4.44 Black and white wherein R 2, R 3, Y, and Z are as defined above in connection with claim 1.
canceled
canceled
Embodiments described in the patent, grouped by the materials and process steps they use.
1 material1 process step
Synthesis of model enediynes: illustrates the general technique for synthesizing the model compound and for the addition of aromatic-alkyne building blocks.
1 process step
Optimization of Cascade Initiation: reaction sequences performed to optimize the initiation of the cyclization reaction.
No measurements recorded
Mechanism of Cascade Initiation: reaction sequence demonstrating the mechanism of cascade initiation of the cyclization reaction.
No measurements recorded
General Procedure for Synthesis of Compounds: describes general laboratory procedures including solvents (THF and hexanes dried over sodium), column chromatography on silica gel (60 Å), NMR conditions (1H at 400/600 MHz, 13C at 100/150 MHz in CDCl₃ and CD₃CN).
2 materials1 process step
General Procedure for protection of 2,3-iodophenol with 'weak link' group (a): suspension of 2,3-iodophenol (0.77 mmol), K₂CO₃ (1.69 mmol), and 18-crown-6 (0.04 mmol) in acetone refluxed; 1,2-dibromoethane (3.06 mmol) added dropwise; purified by flash chromatography to afford compound a.
2 materials1 process step
Procedure for synthesis of 3-iodophenyl diethylcarbamate (b): 3-iodophenol treated with NaH in THF, then N,N-diethylcarbamoyl chloride added; purified by column chromatography to afford compound b.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenyl diethylcarbamate (c): LDA generated from n-BuLi and i-Pr₂NH in THF at 0°C, cooled to -78°C, compound added, then iodine in THF added; workup and column chromatography to afford compound c.
1 material1 process step
Procedure for synthesis of 2,3-diiodophenol (d): carbamate 3 in EtOH treated with excess NaOH under reflux for 5-8 h; workup and column chromatography to afford compound d.
2 materials1 process step
General Procedure for Sonogashira cross coupling of 6 with different substituted acetylenes (1): aryl dihalide (0.59 mmol), PdCl₂(PPh₃)2 (29.70 µmol), CuI (29.70 µmol) in triethylamine; 4-ethynyl-anisole (1.49 mmol, 2.5 equiv.) added; 8 h reaction; purified by flash chromatography to afford compound 1.
2 materials1 process step
General Procedure for radical cascade of (2): bis-methylbenzene (1) (40.00 mg) in benzene, Bu₃SnH (59.70 mg) in benzene, and AIBN (1.53 mg) in benzene; nitrogen degassed; Bu₃SnH and AIBN added by syringe pump over 6 h to refluxing solution; purified by preparatory TLC to afford compound 2.
1 material1 process step
General Procedure for Finkelstein reaction of (3) and (13): sodium iodide added to compound (1c) (55 mg, 0.13 mmol) in acetone, heated to 50°C under nitrogen for 8 h.
Materials described outside the worked examples.
oligo-alkyne compound comprising repeat units of structure (I)
graphene substructures/multicyclic polyaromatic products