CN115611713B - Synthesis method of 9-benzylated fluorenol derivative - Google Patents
Synthesis method of 9-benzylated fluorenol derivative Download PDFInfo
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- AFMVESZOYKHDBJ-UHFFFAOYSA-N fluoren-9-ol Chemical class C1=CC=C2C(O)C3=CC=CC=C3C2=C1 AFMVESZOYKHDBJ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003613 toluenes Chemical class 0.000 claims abstract description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 18
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- JVJZHRVZSLVKDX-UHFFFAOYSA-N C(C1=CC=CC=C1)C1C2=CC=CC=C2C=2C=CC=C(C1=2)O Chemical class C(C1=CC=CC=C1)C1C2=CC=CC=C2C=2C=CC=C(C1=2)O JVJZHRVZSLVKDX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- -1 9-benzyl fluorenone derivative Chemical class 0.000 abstract description 19
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000011282 treatment Methods 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 28
- 238000001228 spectrum Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 125000003107 substituted aryl group Chemical group 0.000 description 10
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000007529 inorganic bases Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- FAWVCJJTDNHNLA-UHFFFAOYSA-N O(C)C1=CC=C(CC2(C3=CC=CC=C3C=3C=CC=CC2=3)O)C=C1 Chemical compound O(C)C1=CC=C(CC2(C3=CC=CC=C3C=3C=CC=CC2=3)O)C=C1 FAWVCJJTDNHNLA-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 150000002220 fluorenes Chemical class 0.000 description 2
- 150000008376 fluorenones Chemical class 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CWGRCRZFJOXQFV-UHFFFAOYSA-N 2,7-dibromofluoren-9-one Chemical compound C1=C(Br)C=C2C(=O)C3=CC(Br)=CC=C3C2=C1 CWGRCRZFJOXQFV-UHFFFAOYSA-N 0.000 description 1
- KXXOMIPLRDTZCC-UHFFFAOYSA-N 2-methylfluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C2=C1 KXXOMIPLRDTZCC-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
The patent application discloses a synthesis method of a 9-benzylated fluorenol derivative. The synthesis method is summarized as follows: toluene derivative, fluorenone and its derivative and one equivalent of inorganic alkali are dissolved in organic solvent, reacted for 24 hours under the irradiation of 12W blue light in air atmosphere, and finally the 9-benzyl fluorenone derivative is obtained through post-treatment, separation and purification. The synthesis method has the remarkable advantages of simplicity and convenience in operation, high yield, high reaction economy, environmental friendliness and the like.
Description
Technical Field
The patent application relates to the technical field of synthesis of organic compounds, in particular to a synthesis method of a 9-benzylated fluorenol derivative.
Background
Fluorene derivatives are of great importance for optoelectronic materials such as Polymer Light Emitting Diodes (PLEDs), polymer solar cells, thin film transistors and photovoltaic cells due to their unique optical, electrical and semiconducting properties (adv. Mater.,2000,12,1737-1750; adv. Mater.,2002,14,477-487;Adv.Optical Mater, 2021,9,2100327; org. Chem. Front.,2021,8,25-31). At the same time, many natural products contain fluorene backbones (org. Lett.,2014,16,282-285; med. Chem. Lett.,2021,36,127824). It is important to develop a more green and efficient synthesis method for synthesizing fluorene-containing frameworks.
However, 9-benzylated fluorenol derivatives are generally synthesized by Grignard reactions (Grignard, V.Compt. Rend.1900,130, 1322.) or carboxylic acid decarboxylation radical coupling (org. Biomol. Chem.,2016,14,9645-9649.) under severe reaction conditions. The above reactions have high operation requirements and poor economy of reaction conditions, and by-products such as metals, carbon dioxide and the like are not friendly to the environment. Although recently researchers reported the synthesis of 9-benzylated fluorenol derivatives by the electrocatalytic dehydration coupling of alcohols with fluorenones (CCS chem.,2022,4,1938-1948.), the process yields are general.
Content of the patent application
To overcome at least one of the problems of the prior art, the present application provides a method for synthesizing a 9-benzylated fluorenol derivative. The method is simple to operate, low in cost, high in yield and environment-friendly. In the patent application, the toluene derivative which is easy to obtain is selected as a benzyl source, the renewable blue light is used for promoting the reaction, a noble metal catalyst is not needed, byproducts which are unfavorable to the environment are not produced, the reaction equipment is simple to operate, the raw materials are easy to obtain, and the industrial production is easy to realize.
In order to solve the technical problems, the technical scheme adopted by the patent application is as follows:
the synthesis method of the 9-benzyl fluorenol derivative is characterized in that toluene derivative, fluorenone and derivatives thereof and one equivalent of inorganic alkali are dissolved in an organic solvent, and then react under the irradiation of blue light in an air atmosphere to prepare the 9-benzyl fluorenol derivative, wherein the molecular structural formulas of the toluene derivative (I) and fluorenone (or derivatives) (II) are as follows:
wherein R is 1 And R is 2 Selected from hydrogen, alkyl, aryl, substituted aryl; r is R 3 And R is 4 Selected from hydrogen, alkyl, halogen, trifluoromethyl.
Preferably, the organic solvent is any one or more of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane and dichloroethane.
Preferably, the molar ratio of toluene derivative to fluorenone (or derivative thereof) is 5:1, and the molar ratio of inorganic base to fluorenone (or derivative thereof) is 1:1.
Preferably, the inorganic base is: any one or more of cesium carbonate, potassium fluoride and cesium fluoride.
Preferably, the blue light irradiation is performed by placing the reaction mixture in a 12W blue light reactor.
Preferably, the number of carbon in the alkyl is 1 or more and 10 or less, and the substituent of the substituted aryl is alkyl, alkoxy or halogen.
More preferably, the alkyl group is methyl, ethyl or isopropyl, the alkoxy group is methoxy or ethoxy, and the halo group is fluoro, chloro or bromo.
Preferably, the temperature of the reaction is 25℃and the pressure of the reaction is 1 atm.
Preferably, the reaction time is 24 hours.
The structural general formula of the 9-benzylated fluorenol derivative (III) in the embodiment of the present application is as follows:
wherein R is 1 And R is 2 Selected from hydrogen, alkyl, aryl, substituted aryl; r is R 3 And R is 4 Selected from hydrogen, alkyl, halogen, trifluoromethyl; the number of carbon in the alkyl is more than or equal to 1 and less than or equal to 10, the substituent of the substituted aryl is alkyl, alkoxy and halogen, and the number of carbon in the aryl and the substituted aryl is more than or equal to 6 and less than or equal to 10.
Compared with the prior art, the invention has the following beneficial effects:
1. the application is that toluene derivative reacts with fluorenone and its derivative under blue light irradiation for the first time to obtain 9-benzyl fluorenone derivative.
2. Compared with the prior method, the method has the advantages of simple reaction equipment and operation. Has the advantages of no generation of by-products which are not friendly to the environment, high conversion rate, easy industrialized production, etc.
3. The method does not need high temperature and noble metal catalysis, and can obtain the 9-benzyl fluorenol derivative with wide application prospect under mild reaction conditions.
Drawings
FIG. 1 nuclear magnetic resonance H-spectrum of 9- (4-methoxybenzyl) -9H-fluoren-9-ol prepared in example 1.
FIG. 2 nuclear magnetic resonance C-spectrum of 9- (4-methoxybenzyl) -9H-fluoren-9-ol prepared in example 1.
FIG. 3 nuclear magnetic resonance H-spectrum of 9- (naphthalen-2-ylmethyl) -9H-fluoren-9-ol prepared in example 2.
FIG. 4 nuclear magnetic resonance C-spectrum of 9- (naphthalen-2-ylmethyl) -9H-fluoren-9-ol prepared in example 2.
FIG. 5 nuclear magnetic resonance H-spectrum of 9- (4-methoxybenzyl) -2-methyl-9H-fluoren-9-ol prepared in example 3.
FIG. 6 nuclear magnetic resonance C-spectrum of 9- (4-methoxybenzyl) -2-methyl-9H-fluoren-9-ol prepared in example 3.
FIG. 7 mass spectrum of 9- (4-methoxybenzyl) -2-methyl-9H-fluoren-9-ol prepared in example 3.
FIG. 8 nuclear magnetic resonance H-spectrum of 2, 7-dibromo-9- (4-methoxybenzyl) -9H-fluoren-9-ol prepared in example 4.
FIG. 9 nuclear magnetic resonance C-spectrum of 2, 7-dibromo-9- (4-methoxybenzyl) -9H-fluoren-9-ol prepared in example 4.
FIG. 10 mass spectrum of 2, 7-dibromo-9- (4-methoxybenzyl) -9H-fluoren-9-ol prepared in example 4.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
It should be noted that:
in this patent application, all the embodiments mentioned herein and the preferred methods of implementation can be combined with each other to form new solutions, if not specifically stated.
In the present patent application, a percentage (%) or part refers to a weight percentage or part by weight with respect to the composition, unless otherwise specified.
In this patent application, the components concerned or their preferred components can be combined with one another to form new solutions, unless otherwise specified.
In this patent application, unless otherwise indicated, the numerical ranges "a-b" represent shorthand representations of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "12-24" means that all real numbers between "12-24" have been listed throughout, and "12-24" is only a shorthand representation of a combination of these values.
The "range" disclosed in this patent application may be in the form of a lower limit and an upper limit, respectively, of one or more lower limits and one or more upper limits.
In this application, unless otherwise indicated, the various reactions or steps may be performed sequentially or sequentially. Preferably, the reaction processes herein are performed sequentially.
Unless otherwise defined, the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any method or material similar or equivalent to those described may be used in the present application.
The inventors of the present patent application have found in the study that one of the methods of synthesis of 9-benzylated fluorenol derivatives in general in the prior art is by Grignard reaction (Grignard, v. Compt. Rend.1900,130, 1322.) under severe reaction conditions, the reaction equation is as follows:
another common method in the prior art for synthesizing 9-benzylated fluorenol derivatives is carboxylic acid decarboxylation radical coupling (org. Biomol. Chem.,2016,14,9645-9649.) synthesis to give 9-benzylated fluorenol derivatives with the following reaction equations:
although recently researchers reported the synthesis of 9-benzylated fluorenol derivatives by the electrocatalytic dehydration coupling of alcohols with fluorenones (CCS chem.,2022,4,1938-1948.), the process yields are generally as follows:
the patent application provides a novel synthesis method of a 9-benzyl fluorenol derivative, which comprises the steps of dissolving toluene derivative, fluorenone and a derivative thereof and an equivalent of inorganic alkali into an organic solvent, and then reacting in an air atmosphere under blue light irradiation to obtain the 9-benzyl fluorenol derivative, wherein the molecular structural formulas of the toluene derivative (I), the fluorenone and a derivative (II) thereof are as follows:
wherein R is 1 And R is 2 Selected from hydrogen, alkyl, aryl, substituted aryl; r is R 3 And R is 4 Selected from hydrogen, alkyl, halogen, trifluoromethyl.
The patent application discloses that under the irradiation of blue light, toluene derivatives and fluorenone and derivatives thereof react to synthesize the 9-benzyl fluorenol derivatives for the first time. Compared with the prior art, the reaction equipment and the operation in the method for preparing the 9-benzylated fluorenol derivative are simple, do not generate by-products which are unfavorable to the environment, have high conversion rate, are easy for industrial production and the like. In addition, the synthesis method does not need high temperature and noble metal catalysis, and the 9-benzyl fluorenol derivative with wide application prospect can be obtained under mild reaction conditions.
In some embodiments, the organic solvent is any one or more of N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, dichloromethane, and dichloroethane.
In some more preferred embodiments, acetonitrile is used as the organic solvent.
In some embodiments, the molar ratio of toluene derivative to fluorenone (or derivative thereof) is 5:1 and the molar ratio of inorganic base to fluorenone (or derivative thereof) is 1:1.
In some embodiments, the inorganic base is: any one or more of cesium carbonate, potassium fluoride and cesium fluoride.
In some more preferred embodiments, cesium fluoride is selected as the inorganic base.
In some embodiments, the blue light irradiation is to place the reaction mixture in a 12W blue light reactor.
In some embodiments, the number of carbons in the alkyl group is 1 or more and 10 or less, and the substituent of the substituted aryl group is alkyl, alkoxy, or halogen.
In some embodiments, the alkyl is methyl, ethyl, or isopropyl, the alkoxy is methoxy or ethoxy, and the halo is fluoro, chloro, or bromo.
In some embodiments, the temperature of the reaction is 25 ℃, and the pressure of the reaction is 1 atm.
In some embodiments, the time of the reaction is 24 hours.
The structural general formula of the 9-benzylated fluorenol derivative (III) in the application is as follows:
wherein R is 1 And R is 2 Selected from hydrogen, alkyl, aryl, substituted aryl; r is R 3 And R is 4 Selected from hydrogen, alkyl, halogen, trifluoromethyl; the number of carbon in the alkyl is more than or equal to 1 and less than or equal to 10, the substituent of the substituted aryl is alkyl, alkoxy and halogen, and the number of carbon in the aryl and the substituted aryl is more than or equal to 6 and less than or equal to 10.
Such substitutions include mono-and di-substitutions.
Next, a method for synthesizing the 9-benzylated fluorenol derivative of the present patent application will be described in detail with specific examples.
1. Preparation example
Example 19 Synthesis and characterization of- (4-methoxybenzyl) -9H-fluoren-9-ol
A10 mL glass bottle was charged with 122.2mg (1.0 mmol) of 4-methoxyanisole, 36.0mg (0.2 mmol) of 9-fluorenone, 30.0mg (0.2 mmol) of cesium fluoride, 2mL of acetonitrile, and stirred under irradiation of 12W blue light for 24 hours. After the reaction, the mixture was concentrated under reduced pressure, and separated by column chromatography to give 54.9mg of pure 9- (4-methoxybenzyl) -9H-fluoren-9-ol as a white solid in 91% yield. The molecular structural formula of the obtained 9- (4-methoxybenzyl) -9H-fluorene-9-alcohol is shown as follows:
the nuclear magnetic resonance H-spectrum and nuclear magnetic resonance C-spectrum of the compound prepared in example 1 are shown in fig. 1 and 2. As can be seen from fig. 1 1 H NMR(400MHz,CDCl 3 ) Delta 7.54 (d, j=7.4 hz, 2H), 7.36-7.21 (m, 6H), 6.90 (d, j=8.7 hz, 2H), 6.67 (d, j=8.7 hz, 2H), 3.74 (s, 3H), 3.23 (s, 2H), 2.16 (br, 1H); the molecular hydrogen spectrum peaks can be in one-to-one correspondence with target products, and the quantity is reasonable. As can be seen from fig. 2: 13 C NMR(101MHz,CDCl 3 ) Delta 158.2,148.3,139.3,131.7,128.9,128.4,127.5,124.2,119.9,112.9,82.3,55.1,44.9. The molecular carbon spectrum peaks can be in one-to-one correspondence with target products, and the number is reasonable. As a result of combining the above nuclear magnetic resonance H spectrum and nuclear magnetic resonance C spectrum, 9- (4-methoxybenzyl) -9H-fluoren-9-ol was obtained as a product of example 1.
The reaction mechanism of the reaction is as follows: the 9-fluorenone generates a diradical species I under the irradiation of blue light, hydrogen atom transfer is generated between the diradical species I and the para-methoxyanisole 2, a benzyl radical species II and a fluorenol alpha carbon radical species III are generated, and finally, radical coupling is carried out between the two radical species to obtain a final target product 3. The reaction mechanism is shown as follows:
example 29 preparation and characterization of naphthalen-2-ylmethyl) -9H-fluoren-9-ol
A10 mL glass bottle was charged with 142.1mg (1.0 mmol) of 2-methylnaphthalene, 36.0mg (0.2 mmol) of 9-fluorenone, 30.0mg (0.2 mmol) of cesium fluoride, 2mL of acetonitrile, and stirred under 12W of blue light for 24 hours. After the reaction, the mixture was concentrated under reduced pressure, and separated by column chromatography to give 50.2mg of 9- (naphthalen-2-ylmethyl) -9H-fluoren-9-ol as a pure product in 78% yield as a white solid. The molecular structural formula of the obtained 9- (4-methoxybenzyl) -2-methyl-9H-fluorene-9-alcohol is shown as follows:
the nuclear magnetic resonance H-spectrum and nuclear magnetic resonance C-spectrum of the compound prepared in example 2 are shown in fig. 3 and 4, respectively. As can be seen from fig. 3: 1 H NMR(400MHz,CDCl 3 ) Delta 7.78-7.72 (m, 1H), 7.68-7.63 (m, 1H), 7.61 (d, j=8.4 hz, 1H), 7.51 (dd, j=7.1, 1.6hz, 2H), 7.45-7.42 (m, 1H), 7.42-7.36 (m, 2H), 7.33-7.27 (m, 4H), 7.25-7.20 (m, 2H), 7.16 (dd, j=8.4, 1.8hz, 1H), 3.44 (s, 2H), 2.23 (br, 1H); the molecular hydrogen spectrum peaks can be in one-to-one correspondence with target products, and the quantity is reasonable. As can be seen from fig. 4: 13 C NMR(101MHz,CDCl 3 ) Delta 148.2,139.3,134.0,133.0,132.2,129.4,129.3,128.9,127.7,127.6,127.5,126.8,125.6,125.3,124.3,119.9,82.4,45.9; the molecular carbon spectrum peaks can be in one-to-one correspondence with target products, and the number is reasonable. As a result of combining the above nuclear magnetic resonance spectrum and the carbon spectrum, it was found that 9- (naphthalen-2-ylmethyl) -9H-fluoren-9-ol was obtained as in example 2.
Example 39 preparation and characterization of- (4-methoxybenzyl) -2-methyl-9H-fluoren-9-ol
A10 mL glass bottle was charged with 122.2mg (1.0 mmol) of 4-methoxyanisole, 38.8mg (0.2 mmol) of 2-methyl-9-fluorenone, 30mg (0.2 mmol) of cesium fluoride, 2mL of acetonitrile, and stirred under 12W blue light irradiation for 24 hours. After the reaction, the mixture was concentrated under reduced pressure, and separated by column chromatography to give 36.0mg of pure 9- (4-methoxybenzyl) -2-methyl-9H-fluoren-9-ol in 57% yield as a white solid. The molecular structural formula of the obtained 9- (4-methoxybenzyl) -2-methyl-9H-fluorene-9-alcohol is shown as follows:
the nuclear magnetic resonance H-spectrum and nuclear magnetic resonance C-spectrum of the compound prepared in example 3 are shown in fig. 5 and 6, respectively. As can be seen from fig. 5: 1 H NMR(400MHz,CDCl 3 ) Delta 7.50 (d, j=7.6 hz, 1H), 7.43 (d, j=8.4 hz, 1H), 7.34-7.27 (m, 1H), 7.23-7.17 (m, 2H), 7.16-7.11 (m, 2H), 6.91 (d, j=8.8 hz, 2H), 6.69 (d, j=8.9 hz, 2H), 3.75 (s, 3H), 3.25 (d, j=13.5 hz, 1H), 3.17 (d, j=13.5 hz, 1H), 2.39 (s, 3H), 2.19 (br, 1H). The molecular hydrogen spectrum peaks can be in one-to-one correspondence with target products, and the quantity is reasonable. As can be seen from fig. 6: 13 C NMR(101MHz,CDCl 3 ) Delta 158.2,148.6,148.1,139.4,137.5,136.6,131.7,129.5,128.7,128.5,126.9,124.9,124.2,119.6,119.5,112.9,82.2,55.1,44.9,21.6; the molecular carbon spectrum peaks can be in one-to-one correspondence with target products, and the number is reasonable. In addition, mass spectrum tests were also performed on the synthesized product, with the following test results: HRMS (ESI-Orbitrap) M/z: [ M-H ] 2 O+H] + calcd for C 22 H 19 O299.1430, found299.1433 As a result of combining the above nuclear magnetic resonance spectrum and a carbon spectrum, 9- (4-methoxybenzyl) -2-methyl-9H-fluoren-9-ol was obtained as a material in example 3.
Example 4 preparation and characterization of 2, 7-dibromo-9- (4-methoxybenzyl) -9H-fluoren-9-ol
A10 mL glass bottle was charged with 122.2mg (1.0 mmol) of 4-methoxyanisole, 67.5mg (0.2 mmol) of 2, 7-dibromo-9-fluorenone, 30mg (0.2 mmol) of cesium fluoride, 2mL of acetonitrile, and stirred under 12W blue light irradiation for 24 hours. After the reaction, the mixture was concentrated under reduced pressure, and separated by column chromatography to give 81.9mg of pure 2, 7-dibromo-9- (4-methoxybenzyl) -9H-fluoren-9-ol as a white solid in 89% yield. The molecular structural formula of the obtained 2, 7-dibromo-9- (4-methoxybenzyl) -9H-fluorene-9-alcohol is shown as follows:
the nuclear magnetic resonance H-spectrum and nuclear magnetic resonance C-spectrum of the compound prepared in example 4 are shown in fig. 8 and 9, respectively. As can be seen from fig. 7: 1 H NMR(400MHz,CDCl 3 ) Delta 7.45 (dd, j=8.0, 1.8hz, 2H), 7.42-7.33 (m, 4H), 6.86 (d, j=8.8 hz, 2H), 6.71 (d, j=8.6 hz, 2H), 3.76 (s, 3H), 3.17 (s, 2H), 2.20 (br, 1H); as can be seen from fig. 8: 13 C NMR(101MHz,CDCl 3 ) Delta 158.6,150.0,137.2,132.1,131.6,127.8,127.3,121.7,121.3,113.2,82.2,55.2,45.0; as can be seen from fig. 9: HRMS (ESI-Orbitrap) M/z theoretical value of 9-benzylated fluorenol derivative compound of the formula (d) is [ M-H ] 2 O+H] + calcd for C 21 H 15 79 Br 2 O440.9484, whereas the actual value obtained by mass spectrometry was 440.9490. As is clear from the results of combining the nuclear magnetic resonance H spectrum, the nuclear magnetic resonance C spectrum and the high-resolution mass spectrum, the product prepared in the example 4 is 2, 7-dibromo-9- (4-methoxybenzyl) -9H-fluorene-9-ol shown in the formula (d), and the compound has a single structure and high purity.
In summary, the present application discloses for the first time that under blue light irradiation, toluene derivatives react with fluorenone and its derivatives to synthesize 9-benzylated fluorenol derivatives. Compared with the prior art, the reaction equipment (glass bottle) in the method for preparing the 9-benzylated fluorenol derivative has the advantages of simple operation (only 12W blue light is needed for stirring), no by-product which is unfavorable to the environment, high conversion rate, easy industrial production and the like.
In addition, the synthesis method of the patent application does not need high temperature and noble metal catalysis, and can obtain the 9-benzyl fluorenol derivative with wide application prospect under mild reaction conditions (namely, the reaction can be carried out under the condition of only 12W blue light irradiation and the reaction can be carried out under the condition of 12W blue light irradiation and the commercially available 12W blue light irradiation). Namely, the toluene derivative which is easy to obtain is selected as a benzyl source, the reaction is promoted by renewable blue light, a noble metal catalyst is not needed, byproducts which are unfavorable to the environment are not produced, the reaction equipment is simple to operate, the raw materials are easy to obtain, and the industrial production is easy to realize.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present patent application. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While several embodiments of the present patent application have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the application, the scope of which is defined by the claims and their equivalents.
Claims (8)
1. The synthesis method of the 9-benzyl fluorenol derivative is characterized in that toluene derivative, fluorenone and a derivative thereof and one equivalent of cesium fluoride are dissolved in acetonitrile and then react under the irradiation of 12W blue light in an air atmosphere to prepare the 9-benzyl fluorenol derivative, wherein the molecular structural formulas of the toluene derivative, the fluorenone and the derivative thereof are as follows:
wherein,R 1 and R is 2 Selected from hydrogen; r is R 3 And R is 4 Selected from hydrogen, alkyl, halogen.
2. The method for synthesizing a 9-benzylated fluorenol derivative according to claim 1, wherein the molar ratio of toluene derivative to fluorenone and its derivative is 5:1, and the molar ratio of cesium fluoride to fluorenone and its derivative is 1:1.
3. The method for synthesizing a 9-benzylated fluorenol derivative according to claim 1, wherein the 12W blue light irradiation is performed by placing the reaction mixture in a 12W blue light reactor.
4. The method for synthesizing a 9-benzylated fluorenol derivative according to claim 1, wherein the number of carbons in the alkyl group is 1 or more and 10 or less.
5. The method for synthesizing a 9-benzylated fluorenol derivative according to claim 4, wherein the alkyl group is methyl, ethyl, or isopropyl, and the halogen group is fluorine, chlorine, or bromine.
6. The method for synthesizing a 9-benzylated fluorenol derivative according to claim 1, wherein the temperature of the reaction is 25 ℃, and the pressure of the reaction is 1 atm.
7. The method for synthesizing a 9-benzylated fluorenol derivative according to claim 1, wherein the reaction time is 24 hours.
8. The method for synthesizing a 9-benzylated fluorenol derivative according to claim 1, wherein the 9-benzylated fluorenol derivative (III) has the following structural formula:
wherein the number of carbon atoms in the alkyl group is 1 or more and 10 or less.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109678788A (en) * | 2019-01-19 | 2019-04-26 | 湘潭大学 | A kind of 1,2- diaryl indoles, derivative and its synthetic method |
| CN110078653A (en) * | 2019-06-10 | 2019-08-02 | 上海兆维科技发展有限公司 | A kind of 9- phenyl fluorene derivative and its preparation method and application that indoles replaces |
| CN110105225A (en) * | 2019-05-15 | 2019-08-09 | 陕西莱特光电材料股份有限公司 | A kind of electroluminescent organic material and the organic electroluminescence device comprising the material |
| CN110128257A (en) * | 2019-05-10 | 2019-08-16 | 华东师范大学 | 1- phenyl -4- amylene -1- ketone derivatives and its synthetic method and application |
| CN113816843A (en) * | 2021-08-17 | 2021-12-21 | 临沂大学 | 2-hydroxy-9-fluorenone derivative and synthesis method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109678788A (en) * | 2019-01-19 | 2019-04-26 | 湘潭大学 | A kind of 1,2- diaryl indoles, derivative and its synthetic method |
| CN110128257A (en) * | 2019-05-10 | 2019-08-16 | 华东师范大学 | 1- phenyl -4- amylene -1- ketone derivatives and its synthetic method and application |
| CN110105225A (en) * | 2019-05-15 | 2019-08-09 | 陕西莱特光电材料股份有限公司 | A kind of electroluminescent organic material and the organic electroluminescence device comprising the material |
| CN110078653A (en) * | 2019-06-10 | 2019-08-02 | 上海兆维科技发展有限公司 | A kind of 9- phenyl fluorene derivative and its preparation method and application that indoles replaces |
| CN113816843A (en) * | 2021-08-17 | 2021-12-21 | 临沂大学 | 2-hydroxy-9-fluorenone derivative and synthesis method and application thereof |
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