CN114573551A - Preparation method of benzo-cyclopentenothiophene compound - Google Patents
Preparation method of benzo-cyclopentenothiophene compound Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 propargyl tertiary alcohol Chemical class 0.000 claims abstract description 17
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 11
- 239000003377 acid catalyst Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- VZFAAPBXHJRMKY-UHFFFAOYSA-N 1-benzothiophene;boric acid Chemical compound OB(O)O.C1=CC=C2SC=CC2=C1 VZFAAPBXHJRMKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- YNCYPMUJDDXIRH-UHFFFAOYSA-N benzo[b]thiophene-2-boronic acid Chemical compound C1=CC=C2SC(B(O)O)=CC2=C1 YNCYPMUJDDXIRH-UHFFFAOYSA-N 0.000 claims description 10
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- VASOMTXTRMYSKD-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boronic acid Chemical compound OB(O)C1=C(F)C(F)=C(F)C(F)=C1F VASOMTXTRMYSKD-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- KWNPRVWFJOSGMZ-UHFFFAOYSA-N 2-boronobenzoic acid Chemical compound OB(O)C1=CC=CC=C1C(O)=O KWNPRVWFJOSGMZ-UHFFFAOYSA-N 0.000 claims description 3
- LBUNNMJLXWQQBY-UHFFFAOYSA-N 4-fluorophenylboronic acid Chemical compound OB(O)C1=CC=C(F)C=C1 LBUNNMJLXWQQBY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 56
- METKIMKYRPQLGS-UHFFFAOYSA-N atenolol Chemical compound CC(C)NCC(O)COC1=CC=C(CC(N)=O)C=C1 METKIMKYRPQLGS-UHFFFAOYSA-N 0.000 description 20
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 2
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- TUNLYEHIVPWOHK-ONEGZZNKSA-N (e)-2-methylbut-2-enoyl chloride Chemical compound C\C=C(/C)C(Cl)=O TUNLYEHIVPWOHK-ONEGZZNKSA-N 0.000 description 1
- SRWDQSRTOOMPMO-UHFFFAOYSA-N 3-bromo-1-benzothiophene Chemical compound C1=CC=C2C(Br)=CSC2=C1 SRWDQSRTOOMPMO-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- RYXZOQOZERSHHQ-UHFFFAOYSA-N [2-(2-diphenylphosphanylphenoxy)phenyl]-diphenylphosphane Chemical compound C=1C=CC=C(P(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RYXZOQOZERSHHQ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000001773 anti-convulsant effect Effects 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002365 anti-tubercular Effects 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940121657 clinical drug Drugs 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- WCOOTBDRCHTKSY-UHFFFAOYSA-N cyclopentanethione Chemical class S=C1CCCC1 WCOOTBDRCHTKSY-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a preparation method of benzo-cyclopentenothiophene compounds, which is characterized in that propargyl tertiary alcohol shown in a formula I is used as a raw material, the propargyl tertiary alcohol and benzothiophene boric acid are catalyzed by an organic acid catalyst to perform cyclization reaction in an organic solvent at room temperature in an inert atmosphere environment, and reaction products are separated and purified to obtain the benzo-cyclopentenothiophene compounds. The process method has good universality and can be used for preparing various benzo-cyclopentenothiophene derivative products; has the characteristics of safety, greenness and low price.
Description
Technical Field
The invention relates to the technical field of organic synthesis, and particularly relates to a preparation method of a benzo-cyclopentenothiophene compound.
Background
In the fields of pharmaceutical and synthetic chemistry, many natural and synthetic molecules with known therapeutic potential have a multi-substituted benzothiophene backbone, and the synthesis of such structures and their derivatives is a focus of research. The benzothiophene ring with unique lipophilicity can be used for deriving medicaments for treating various diseases after being substituted. In the process of developing new drugs, benzothiophene derivatives are used as lead compounds to synthesize novel drug molecules with pharmacological activity, and the method has very important significance for the current research and development of medicines. Benzo cyclopentenothiophene (benzo b cyclopenta d thiophene) is one of the superior structures found in the medicine, has various biological activities, and can play the roles of antimicrobial, anticancer, anti-inflammatory, antioxidant, antituberculosis, antidiabetic, anticonvulsant and the like. In addition, many benzocyclopenthiophenes have high therapeutic effects as clinical drugs, and have been widely used for the treatment of various types of diseases. Benzothiophene derivatives are also widely used in other fields, and various benzothiophene-based compounds have been used in organic photoelectric materials and organic semiconductors.
Currently substituted benzothiophenes can be achieved by cyclization or functionalization of the benzothiophene. Because the C-H bond at the C2 position of benzothiophene is strongly acidic, the method of introducing a carbon substituent at the C2 position often requires stoichiometric metalation reactions and the use of strongly basic metal-organic reagents. In addition, Friedel-crafts alkylation is also commonly used to prepare substituted benzothiophene compounds, however such reactions tend to yield mixtures of C2 and C3 substitutions. The construction of benzocyclopentenothiophenes has been considered a challenging topic. The literature Tetrahedron,2006,62,11513 reports that metallic palladium catalyzes the intramolecular cyclization reaction of a cyclopentanethione derivative to construct a benzocyclopentathiopheno structure, the reaction requires the use of air-sensitive DPEphos as a ligand and high-temperature heating (100 ℃). Patent CN108250252A discloses a method for synthesizing benzocyclopentathiophenes compound by multi-step reaction of benzothiophene and methacrylic acid using phosphorus pentoxide as catalyst. KR2021038357A discloses a process for the construction of this structure by a three-step reaction of benzothiophene with (E) -2-methyl-2-butenoyl chloride, using cuprous cyanide as catalyst. Patent WO2019022569 a1 discloses a method for synthesizing benzocyclopentaenothiophene derivatives by catalyzing cyclization reaction of 3-bromobenzothiophene and phenyl Grignard reagent by metal nickel. In the synthesis process of the benzo-cyclopentenothiophene compound, a noble metal catalyst and a multi-step reaction are usually required in the reaction, so that the cost is high and the operation is complicated.
Disclosure of Invention
The invention aims to provide a preparation method of a benzocyclopentenothiophene compound, which takes propargyl tertiary alcohol and benzothiophene boric acid as raw materials, completes the construction of a benzocyclopentenothiophene framework under the conditions of organic acid catalysis and room temperature, and has the advantages of high operability and high reaction selectivity.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of benzo-cyclopentenothiophene compounds takes propargyl tertiary alcohol shown in a formula I as a raw material, and is catalyzed by an organic acid catalyst in an organic solvent to perform cyclization reaction with benzothiophene boric acid in an inert atmosphere at room temperature, and reaction products are obtained through separation and purification;
the invention discloses a novel method for synthesizing benzocyclopentenothiophene compounds through cyclization reaction of propargyl tertiary alcohol and benzothiophene boric acid. The method has the characteristics of good operability and stability, mild reaction conditions, no need of water-free and oxygen-free treatment, high catalytic efficiency, easy separation of products and the like.
Preferably, the molar ratio of the materials in the cyclization reaction is propargyl tertiary alcohol: benzothiopheneboronic acid: organic acid catalyst: organic solvent ═ 1: 1-3: 0.01-0.2: 5.0-10.0.
Preferably, the reaction temperature of the cyclization reaction is controlled to 20 to 100 ℃.
Preferably, the organic acid catalyst is selected from one or two of diphenyl phosphate, p-fluorobenzeneboronic acid, pentafluorophenylboronic acid, o-carboxyphenylboronic acid, p-toluenesulfonic acid, benzoic acid and trifluoroacetic acid.
Preferably, the organic solvent is one of dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, dioxane, nitromethane and tetrahydrofuran.
Preferably, the inert gas atmosphere is a gas atmosphere composed of nitrogen or argon.
Preferably, R is1One or more selected from hydrogen, alkyl, alkoxy, aryl and trisubstituted silicon base; the R is2One or more selected from alkyl and aryl; said R is3One or more selected from alkyl and aryl.
Preferably, the R is selected from one or more of hydrogen, halogen, alkyl, alkoxy, aryl, nitro, amine, ester, aldehyde, hydroxyl and sulfonic acid.
Preferably, R is located at the 4, 5, 6 or 7 position of the benzothiopheneboronic acid. R can independently be selected from 4, 5, 6 or 7; r can be one substituent or two substituents, and the substituent types can be the same or different.
The invention has the beneficial effects that: can be finished under conventional conditions, the one-pot reaction does not need to replace the solvent midway, and has high reaction operability and high reaction yield; the process method has good universality and can be used for preparing various benzo-cyclopentylthiophene compounds; has the characteristics of safety, greenness and low price.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
General description of the embodiments
A preparation method of benzo-cyclopentenothiophene compounds takes propargyl tertiary alcohol shown in a formula I as a raw material, and is catalyzed by an organic acid catalyst in an organic solvent to perform cyclization reaction with benzothiophene boric acid in an inert atmosphere at room temperature, and reaction products are obtained through separation and purification;
the organic acid catalyst is selected from one or two of diphenyl phosphate, p-fluorobenzeneboronic acid, pentafluorophenylboronic acid, o-carboxyphenylboronic acid, p-toluenesulfonic acid, benzoic acid and trifluoroacetic acid. The inert atmosphere is a gas environment consisting of nitrogen or argon. The organic solvent is one of dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, dioxane, nitromethane and tetrahydrofuran. The molar use ratio of all materials in the cyclization reaction is propargyl tertiary alcohol: benzothiopheneboronic acid: organic acid catalyst: organic solvent ═ 1: 1-3: 0.01-0.2: 5.0-10.0. The reaction temperature of the cyclization reaction is controlled to be 20-100 ℃.
The R is1One or more selected from hydrogen, alkyl, alkoxy, aryl and trisubstituted silicon base; the R is2One or more selected from alkyl and aryl; the R is3One or more selected from alkyl and aryl; r is selected from one or more of hydrogen, halogen, alkyl, alkoxy, aryl, nitro, amino, ester group, aldehyde group, hydroxyl and sulfonic group; and R is 4, 5, 6 or 7 position of benzothiopheneboronic acid. R may independently be selected from 4, 5, 6 or 7; r can be one substituent or two substituents, and the substituent types can be the same or different.
Example 1 Synthesis of N- (4- (1,3-diphenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl-) acetamide in a 5mL dry sealed tube, diphenyl phosphate (5.0mg,10 mol%), N- (4- (1-hydroxy-1, 3-diphenyl-2-propynyl-1-) phenyl) acetamide (68mg,0.20mmol), benzothiophene-2-boronic acid (43mg,0.24mmol), and 2.0 mL of 1, 2-dichloroethane were sequentially added, and the mixture was allowed to react at 35 ℃ for 36 hours under a nitrogen atmosphere.
After the reaction was completed, 5ml of a saturated aqueous sodium bicarbonate solution was added to quench the reaction, dichloromethane was extracted, the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a crude product. And (4) separating and purifying the crude product by silica gel column chromatography, and concentrating to obtain the product. The yield thereof was found to be 86%.1H-NMR(400MHz,CDCl3):δ7.83-7.81(1H,m),7.75-7.72(1H,m),7.66(2H,td,J＝6.8,1.6Hz),7.50-7.46(2H,m),7.44-7.38(3H,m),7.37-7.34(2H,m),7.32-7.29(2H,m),7.28-7.27(3H,m),7.26-7.24(2H,m),7.11(1H,brs,N-H),6.83(1H,s),2.15(3H,s).13C-NMR(100MHz,CDCl3):δ168.4,154.2,145.8,143.3,142.7,141.3,139.9,138.7,136.8,135.7,133.2,132.7,128.6,128.4,128.2,128.0,127.8,127.1,124.4,123.7,123.6,122.9,120.1,64.8,24.5.IR(KBr):ν＝3399,3057,2927,1667,1660,1512,1427,1317,1072,1020,832,757cm–1.HRMS(ESI-TOF):calcd.for C31H24NOS+(M+H)+:458.1578,found:458.1569。
Example 2 Synthesis of Nitrogen- (4- (3-phenyl-1-p-tolyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl-) acetamide in a 5mL dry sealed tube was added diphenyl phosphate (5.0mg,10 mol%), nitrogen- (4- (1-hydroxy-1-phenyl-3-p-tolyl 2-propynyl-1-) phenyl) acetamide (72mg,0.20mmol), benzothiophene-2-boronic acid (43mg,0.24mmol), and 2.0 mL of 1, 2-dichloroethane sequentially, and the mixture was allowed to react at 35 ℃ for 36 hours under a nitrogen atmosphere.
After the reaction was completed, 5ml of a saturated aqueous sodium bicarbonate solution was added to quench the reaction, dichloromethane was extracted, the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a crude product. And (4) separating and purifying the crude product by silica gel column chromatography, and concentrating to obtain the product. The yield thereof was found to be 87%.1H-NMR(400MHz,CDCl3):δ7.80(1H,dd,J＝6.4,2.4Hz),7.77(1H,dd,J＝6.0,2.0Hz),7.56(2H,d,J＝8.0Hz),7.42-7.39(2H,m),7.35(2H,d,J＝8.4,2.0Hz),7.30-7.21(9H,m),6.79(1H,s),2.44(3H,s),2.16(3H,s).13C-NMR(100MHz,CDCl3):δ168.5,154.2,145.9,143.0,142.9,141.4,140.1,138.9,137.9,136.9,132.9,129.2,128.7,128.5,128.2,127.9,127.2,126.3,124.4,123.8,123.7,123.0,120.2,64.8,24.6,21.4.IR(KBr):ν＝3302,3056,2924,2857,1668,1601,1511,1405,1317,1184,1071,1019,829,760cm–1.HRMS(ESI-TOF):calcd.for C32H26NOS+(M+H)+:472.1735,found:472.1722。
Example 31 Synthesis of 1, 3-triphenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene
To a 5mL dry sealed tube were added diphenyl phosphate (5.0mg,10 mol%), 1,1, 3-triphenyl-2-propynyl-1-ol (56mg,0.20mmol), benzothiophene-2-boronic acid (43mg,0.24mmol), and 2.0 mL of 1, 2-dichloroethane in this order, and the mixture was reacted at 35 ℃ for 36 hours under a nitrogen atmosphere.
After the reaction was completed, 5ml of a saturated aqueous sodium bicarbonate solution was added to quench the reaction, dichloromethane was extracted, the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to obtain a crude product. And (3) separating and purifying the crude product by silica gel column chromatography, and concentrating to obtain the product. The yield thereof was found to be 82%.1H-NMR(400MHz,CDCl3):δ7.81-7.78(1H,m),7.73-7.70(1H,m),7.65(2H,dt,J＝6.8,1.6Hz),7.47-7.43(2H,m),7.41-7.37(2H,m),7.35-7.32(4H,m),7.28(2H,t,J＝2.0Hz),7.25-7.22(5H,m),6.84(1H,s).13C-NMR(100MHz,CDCl3):δ154.2,145.9,143.4,142.9,141.4,139.9,136.3,135.8,132.8,128.6,128.6,128.6,128.4,128.2,128.0,127.8,127.7,127.1,124.3,123.7,123.6,122.9,65.3.IR(KBr):ν＝3056,2924,2853,1598,1491,1445,1264,1071,1028,898,754cm–1.HRMS(ESI-TOF):calcd.for C29H20S+(M)+:400.1286,found:400.1274；HRMS(APCI-TOF):calcd.For C29H21S+(M+H)+:401.1364,found:401.1360。
Starting from the respective substituted propargyl tertiary alcohol derivative and benzothiophene-2-boronic acid, benzocyclopentenothiophene derivatives were obtained under the conditions described above, the results of which are shown in the following table:
| compound numbering | Yield (%) |
| 4 | 84 |
| 5 | 64 |
| 6 | 85 |
| 7 | 81 |
| 8 | 89 |
| 9 | 82 |
| 10 | 67 |
| 11 | 77 |
| 12 | 84 |
| 13 | 68 |
| 14 | 71 |
。
N- (4- (3-Phenyl-1-m-tolyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) Phenyl-) acetamide (N- (4- (3-Phenyl-1- (m-tolyl) -3H-benzoa [ b ] cyclopenta [ d ] thiophen-3-yl) Phenyl) acetamide) (4).
1H-NMR(400MHz,CDCl3):δ7.84-7.81(1H,m),7.77-7.74(1H,m),7.49-7.47(2H,m),7.43-7.39(3H,m),7.36(3H,dt,J＝8.4,1.6Hz),7.32-7.27(6H,m),7.25-7.23(2H,m),6.82(1H,s),2.44(3H,s),2.14(3H,s).13C-NMR(100MHz,CDCl3):δ168.4,154.2,146.0,143.3,142.9,141.5,140.1,138.9,138.2,136.9,135.8,132.9,129.0,128.9,128.7,128.6,128.4,127.9,127.2,125.4,124.5,123.8,123.7,123.0,120.2,64.9,24.6,21.6.IR(KBr):ν＝3304,3057,2924,2854,1667,1601,1511,1404,1317,1185,1079,1020,838,785cm– 1.HRMS(ESI-TOF):calcd.for C32H26NOS+(M+H)+:472.1735,found:472.1724。
N- (4- (3-phenyl-1-o-tolyl-3H-benzo [ b)]Cyclopenteno [ d ]]Thiophene-3-) Phenyl-) acetamide (N- (4- (3-Phenyl-1- (o-tolyl) -3H-benzol [ b ]]cyclopenta[d]thiophen-3-yl)phenyl)acetamide)(5)。1H-NMR(400MHz,CDCl3):δ7.85(1H,d,J＝7.6Hz),7.50-7.48(2H,m),7.46-7.41(4H,m),7.40-7.37(4H,m),7.36-7.32(3H,m),7.29-7.27(2H,m),7.24-7.23(2H,m),6.78(1H,s),2.35(3H,s),2.22(3H,s).13C-NMR(100MHz,CDCl3):δ168.5,153.0,145.7,143.5,142.8,141.3,140.2,138.8,136.8,136.5,135.5,132.8,130.1,129.4,128.6,128.4,128.1,127.8,127.1,125.8,124.5,123.7,123.5,121.8,120.2,65.2,24.5,20.3.IR(KBr):ν＝3303,3057,2925,2853,1668,1601,1538,1404,1317,1185,1069,1018,834,758cm–1.HRMS(ESI-TOF):calcd.for C32H26NOS+(M+H)+:472.1735,found:472.1724。
N- (4- (1- (4-Methoxyphenyl) -3-phenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl-) acetamide (N- (4- (1- (4-Methoxyphenyl) -3-phenyl-3H-benzol [ b ] cyclopenta [ d ] thiophen-3-yl) phenyl) acetamide) (6).
1H-NMR(400MHz,CDCl3):δ7.85-7.83(1H,m),7.80-7.77(1H,m),7.62(2H,dt,J＝8.4,2.0Hz),7.44-7.42(2H,m),7.38-7.35(2H,m),7.33(1H,s),7.32-7.29(4H,m),7.28-7.24(3H,m),7.03(2H,dt,J＝8.8,2.0Hz),6.79(1H,s),3.91(3H,s),2.17(3H,s).13C-NMR(100MHz,CDCl3):δ168.4,159.7,154.2,146.0,143.0,142.5,141.0,140.3,139.0,136.9,132.9,129.5,128.7,128.6,128.3,127.9,127.2,124.4,123.8,123.7,123.0,120.2,114.0,64.8,55.5,24.6.IR(KBr):ν＝3308,3057,2960,2855,1667,1632,1604,1506,1317,1176,1080,1030,836,760cm–1.HRMS(ESI-TOF):calcd.for C32H26O2NS+(M+H)+:488.1684,found:488.1674。
N- (4- (1- (3-Methoxyphenyl) -3-phenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl-) acetamide (N- (4- (1- (3-Methoxyphenyl) -3-phenyl-3H-benzob ] cyclopenta [ d ] thiophen-3-yl) phenyl) acetamide) (7).
1H-NMR(400MHz,CDCl3):δ7.82-7.80(1H,m),7.79-7.77(1H,m),7.42-7.38(3H,m),7.44-7.42(2H,m),7.36-7.32(3H,m),7.30-7.26(5H,m),7.25-7.23(3H,m),7.19-7.18(1H,m),6.96(1H,dd,J＝8.0,3.2Hz),6.83(1H,s),3.85(3H,s),2.13(3H,s).13C-NMR(100MHz,CDCl3):δ168.4,160.0,154.3,146.0,143.5,142.8,141.3,139.9,138.8,137.2,137.0,132.8,129.6,128.7,128.6,127.9,127.3,124.5,123.8,123.7,123.1,120.8,120.2,114.1,113.6,64.9,55.5,24.6.IR(KBr):ν＝3308,3057,2927,2854,1667,1600,1531,1404,1317,1182,1070,1036,838,760cm–1.HRMS(ESI-TOF):calcd.for C32H26O2NS+(M+H)+:488.1684,found:488.1673。
N- (4- (1- (4-Chlorophenyl) -3-phenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl-) acetamide (N- (4- (1- (4-Chlorophenyl) -3-phenyl-3H-benzo [ b ] cyclopenta [ d ] thiophen-3-yl) phenyl) acetamide) (8).
1H-NMR(400MHz,CDCl3):δ7.72-7.70(1H,m),7.58-7.54(1H,m),7.48(2H,td,J＝8.4,2.0Hz),7.35-7.32(2H,m),7.31-7.29(2H,m),7.23-7.21(3H,m),7.19-7.17(4H,m),7.16-7.13(3H,m),6.71(1H,s),2.04(3H,s).13C-NMR(100MHz,CDCl3):δ167.5,153.3,144.8,142.6,141.4,139.1,138.3,137.5,135.7,133.1,132.9,131.5,128.4,127.6,127.6,127.3,126.7,126.2,123.4,123.1,122.7,122.6,121.5,119.1,63.8,23.4.IR(KBr):ν＝3303,3058,2926,2855,1668,1601,1514,1404,1317,1185,1090,1015,834,760cm–1.HRMS(ESI-TOF):calcd.for C31H23ClNOS+(M+H)+:492.1189,found:492.1176。
N- (4- (1- (3-Chlorophenyl) -3-phenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl-) acetamide (N- (4- (1- (3-Chlorophenyl) -3-phenyl-3H-benzo [ b ] cyclopenta [ d ] thiophen-3-yl) phenyl) acetamide) (9).
1H-NMR(400MHz,CDCl3):δ7.83(1H,dd,J＝7.2,2.4Hz),7.83(1H,dd,J＝7.2,2.4Hz),7.66-7.65(1H,m),7.56-7.54(1H,m),7.43(1H,s),7.42-7.38(3H,m),7.35-7.32(2H,m),7.31-7.29(4H,m),7.28-7.23(4H,m),6.86(1H,s),2.15(3H,s).13C-NMR(100MHz,CDCl3):δ168.7,154.5,145.9,144.2,142.5,140.1,139.3,138.5,137.6,137.0,134.5,132.6,129.8,128.8,128.5,128.3,128.2,127.8,127.4,126.4,124.6,123.9,123.8,122.7,120.3,65.0,24.6.IR(KBr):ν＝3307,3058,2926,2854,1668,1601,1404,1317,1264,1185,1080,1020,834,759cm–1.HRMS(ESI-TOF):calcd.for C31H23ClNOS+(M+H)+:492.1189,found:492.1178。
N- (4- (1- (2-Chlorophenyl) -3-phenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl-) acetamide (N- (4- (1- (2-Chlorophenyl) -3-phenyl-3H-benzo [ b ] cyclophen [ d ] thiophen-3-yl) phenyl) acetamide) (10).
1H-NMR(400MHz,CDCl3):δ7.79(1H,dd,J＝6.4,2.0Hz),7.54(1H,dd,J＝7.6,1.6Hz),7.50-7.46(2H,m),7.44-7.40(3H,m),7.39-7.36(3H,m),7.35-7.31(3H,m),7.30-7.27(3H,m),7.25-7.21(2H,m),6.86(1H,s),2.15(3H,s).13C-NMR(100MHz,CDCl3):δ168.7,154.5,145.9,144.2,142.5,140.1,139.3,138.5,137.6,137.0,134.5,132.6,129.8,128.8,128.5,128.3,128.2,127.8,127.4,126.4,124.6,123.9,123.8,122.7,120.3,65.0,24.6.IR(KBr):ν＝3306,3057,2925,2854,1670,1600,1510,1405,1317,1185,1020,834,759cm–1.HRMS(ESI-TOF):calcd.for C31H23ClNOS+(M+H)+:492.1189,found:492.1176。
N- (4- (1- (cyclopropyl-3-phenyl-3H-benzo [ b ]]Cyclopenteno [ d ]]Thiophene-3-) phenyl-) acetamide (N- (4- (1-Cyclopropyl-3-phenyl-3H-benzol [ b ]]cyclopenta[d]thiophen-3-yl)phenyl)acetamide)(11).1H-NMR(400MHz,CDCl3):δ8.13(1H,d,J＝8.0Hz),7.81(1H,d,J＝8.4Hz),7.41-7.36(4H,m),7.28(2H,t,J＝7.6Hz),7.25-7.22(4H,m),7.21-7.16(2H,m),6.39(1H,d,J＝1.6Hz),2.14(3H,s),2.10-2.02(1H,m),0.99-0.95(2H,m),0.75-0.71(2H,m).13C-NMR(100MHz,CDCl3):δ168.5,153.0,145.9,143.1,142.7,142.1,139.3,138.8,136.7,133.3,128.6,128.4,127.8,127.1,124.6,123.8,123.7,122.3,120.2,64.2,24.6,10.1,6.79,6.76.IR(KBr):ν＝3305,3058,2926,2855,1670,1599,1511,1405,1317,1185,1020,975,833,760cm–1.HRMS(ESI-TOF):calcd.for C28H24NOS+(M+H)+:422.1579,found:422.1567。
N- (4- (1,3-Diphenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl) -4-methylbenzenesulfonamide (N- (4- (1,3-Diphenyl-3H-benzo [ b ] cyclopenta [ d ] thiophen-3-yl) phenyl) -4-methylb enzenesulfonamide) (12).
1H-NMR(400MHz,CDCl3):δ7.84-7.80(1H,m),7.75-7.71(1H,m),7.66-7.62(4H,m),7.50-7.45(2H,m),7.44-7.40(1H,m),7.30-7.26(6H,m),7.25-7.21(5H,m),6.95(2H,dt,J＝8.8,2.8Hz),6.78(1H,s),6.41(1H,brs,N-H),2.37(3H,s).13C-NMR(100MHz,CDCl3):δ154.0,145.9,144.0,143.2,142.6,141.6,140.0,139.9,136.4,135.7,135.6,132.8,129.8,128.9,128.7,128.6,128.2,127.8,127.4,127.3,124.5,123.8,123.8,123.0,121.6,64.7,21.7.IR(KBr):ν＝3256,3056,2926,1632,1599,1506,1385,1333,1161,1091,1019,922,812,757cm–1.HRMS(ESI-TOF):calcd.for C36H28O2NS2 +(M+H)+:570.1561,found:570.1551。
4-Methyl-N- (4- (3-Methyl-1-phenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene-3-) phenyl) benzenesulfonamide (4-Methyl-N- (4- (3-Methyl-1-phenyl-3H-benzo [ b ] cyclopenta [ d ] thiophen-3yl) phenyl) benzanesulfonamide) (13).
1H-NMR(400MHz,CDCl3):δ7.85-7.82(1H,m),7.74-7.70(1H,m),7.67-7.59(4H,m),7.47(2H,t,J＝7.6Hz),7.41(1H,t,J＝7.2Hz),7.30-7.27(4H,m),7.24-7.21(2H,m),6.97(2H,dd,J＝6.4,2.0Hz),6.63(1H,brs),6.52(1H,s),2.37(3H,s),1.80(3H,s).13C-NMR(100MHz,CDCl3):δ156.2,145.5,144.8,143.9,140.9,138.9,136.5,136.0,135.4,133.0,131.8,129.8,128.6,128.2,128.1,127.4,127.3,124.5,123.9,123.6,122.8,121.9,55.4,24.4,21.7.IR(KBr):ν＝3254,3057,2961,2924,2853,1631,1599,1511,1463,1335,1161,1092,920,814,759cm–1.HRMS(ESI-TOF):calcd.for C31H26NO2S2 +(M+H)+:508.1405,found:508.1391。
3-Methyl-1,3-diphenyl-3H-benzo [ b ] cyclopenteno [ d ] thiophene (3-Methyl-1,3-diphenyl-3H-benzo [ b ] cyclopentha [ d ] thiophene) (14)
1H-NMR(400MHz,CDCl3):δ7.86-7.84(1H,m),7.76-7.74(1H,m),7.67(2H,d,J＝6.8Hz),7.48(2H,t,J＝8.0Hz),7.44-7.40(3H,m),7.33-7.27(4H,m),7.24-7.22(1H,m),6.62(1H,s),1.88(3H,s).13C-NMR(100MHz,CDCl3):δ156.3,145.4,145.0,141.7,140.7,139.2,136.1,132.9,128.6,128.4,128.1,127.8,126.9,126.2,124.3,123.8,123.3,122.7,55.9,24.4.IR(KBr):ν＝3058,2964,2924,2852,1631,1601,1493,1265,1186,1080,1025,829,755cm–1.HRMS(ESI-TOF):calcd.for C24H19S+(M+H)+:339.1207,found:339.1197。
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (9)
1. A preparation method of benzo-cyclopentenothiophene compounds is characterized in that propargyl tertiary alcohol shown in a formula I is used as a raw material, cyclization reaction is carried out on the propargyl tertiary alcohol and benzothiophene boric acid in an organic solvent under the catalysis of an organic acid catalyst at room temperature in an inert atmosphere environment, and reaction products are obtained through separation and purification;
2. the process according to claim 1, wherein the cyclization reaction is carried out in a molar ratio of propargyl tertiary alcohol: benzothiopheneboronic acid: organic acid catalyst: organic solvent ═ 1: 1-3: 0.01-0.2: 5.0-10.0.
3. The production method according to claim 1, wherein the reaction temperature of the cyclization reaction is controlled to 20 to 100 ℃.
4. The preparation method according to claim 1, wherein the organic acid catalyst is one or two selected from diphenyl phosphate, p-fluorobenzeneboronic acid, pentafluorophenylboronic acid, o-carboxyphenylboronic acid, p-toluenesulfonic acid, benzoic acid and trifluoroacetic acid.
5. The method according to claim 1, wherein the organic solvent is one of dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, dioxane, nitromethane, and tetrahydrofuran.
6. The method according to claim 1, wherein the inert gas atmosphere is a gas atmosphere composed of nitrogen or argon.
7. The method of claim 1, wherein R is1One or more selected from hydrogen, alkyl, alkoxy, aryl and trisubstituted silicon base; the R is2One or more selected from alkyl and aryl; the R is3One or more selected from alkyl and aryl.
8. The preparation method of claim 1, wherein R is selected from one or more of hydrogen, halogen, alkyl, alkoxy, aryl, nitro, amine, ester, aldehyde, hydroxyl and sulfonic acid.
9. The method according to claim 1, wherein R is at the 4-, 5-, 6-or 7-position of benzothiopheneboronic acid.
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