CN111116337B - Synthesis method of spiro compound - Google Patents

Synthesis method of spiro compound Download PDF

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CN111116337B
CN111116337B CN201911425368.1A CN201911425368A CN111116337B CN 111116337 B CN111116337 B CN 111116337B CN 201911425368 A CN201911425368 A CN 201911425368A CN 111116337 B CN111116337 B CN 111116337B
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CN111116337A (en
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白璐
栾新军
吴娇瑜
张乃琛
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Northwest University
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    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
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Abstract

The invention takes simple and commercialized double halide 1, alkyne 2 and 2-naphthol compound 3 as raw materials to prepare the product through reaction by [2+2+1]]Construction of Spiro [4.5] by domino coupling reaction]A cyclic compound. Three simple raw materials are adopted, so that the challenge of difficult substrate synthesis in the traditional method is avoided; under the simplest condition, only a transition metal palladium catalyst is added, and no additional oxidant or ligand is needed, so that the reaction cost is reduced; the method has the advantages of wide substrate application range, mild reaction conditions, high conversion rate, high yield, good purity of the prepared product and wide industrial production prospect, and provides a new method for the fields of medicines, natural product synthesis, luminescent materials and the like.

Description

Synthesis method of spiro compound
Technical Field
The invention relates to a method for synthesizing a spiro compound, belonging to the technical field of organic synthesis.
Background
The spiro skeleton is ubiquitous in natural products and drug molecules, and is the core skeleton of many molecules with pharmacological activity. Because the catalyst has the advantages of structural rigidity, good stability and the like, the catalyst also shows attractive application prospects in the fields of asymmetric catalysis, photoelectric materials and the like. In recent years, this field has been paid much attention by scientists, and scholars at home and abroad have conducted a great deal of exploratory research work in this field to construct thousands of spiro-skeleton compounds. However, for the construction of complex spiro molecules, a functionalized substrate prepared in multiple steps is generally used or the construction is carried out ring by ring, the steps are long, and the types of products are very limited. Therefore, how to realize the efficient construction of spiro molecular frameworks with novel structures and different functions has attracted great attention of synthetic chemists.
The key step of the dearomatization spiro cyclization reaction formed by carbon-carbon bond or carbon-heterobond catalyzed by transition metal to break aromaticity is sp2Conversion of a planar two-dimensional structure of carbon to contain sp3A partially saturated three-dimensional stereo structure of carbon. In the existing synthesis method, the transition metal catalyzed dearomatization spiro cyclization reaction of aromatic compounds is mainly carried out through two routes: 1) the intramolecular dearomatization spiro cyclization reaction strategy has the advantages of high chemical selectivity, strong functional group tolerance and the like. Unfortunately, such reactions are generally limited to intramolecular processes and require pre-functionalization of the substrate. 2) The dearomatization spiro cyclization reaction of the biaryl phenol compound and the unsaturated system is carried out, the biaryl compound of the reaction is generally obtained by a method such as Suzuki coupling, and the coupling fragment is generally limited to the unsaturated system such as alkyne, so that the development of the method is greatly limited.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing a spiro compound, which overcomes the defects that the substrate synthesis of the existing spiro compound synthesis method is difficult, the functionalization at the later stage is difficult, the reaction condition is harsh, the applicable substrate is limited, and the like, and the synthesis method is not suitable for industrial production.
The invention is realized as follows:
a synthesis method of spiro [4.5] compound comprises adding a double halide 1, alkyne 2 and 2-naphthol compound 3 shown in the following formula into a reaction solvent 1, 4-dioxane, reacting under the protection of inert gas, separating and purifying to obtain spiro compound 4;
Figure DEST_PATH_IMAGE002
wherein R is selected from hydrogen, alkoxy of C1-C4, halogen, ester group of C2-C4, trifluoromethoxy and cyano; r1、R2Independently selected from C1-C4 alkyl, C2-C5 alkenyl, TMS, TES, -CH2OTBS, thienyl, phenyl or substituted phenyl, wherein the substituent in the substituted phenyl is C1-C4 alkyl, C1-C4 alkoxy, halogen, C2-C4 ester group or C2-C4 acyl; r' is selected from hydrogen, alkoxy of C1-C4, ester group of C2-C4, acyl of C2-C4, halogen, OTBS, thienyl, cyano or phenyl; x, X' are independently selected from halogens.
The molar ratio of the double halogen compound 1, the alkyne 2 and the 2-naphthol compound 3 is (1-2): 1-2).
The conditions are as follows: palladium acetate is used as a catalyst, potassium phosphate is used as alkali, the dosage is 2-3 times, and the reaction temperature is 100-150 ℃.
Further, the reaction does not require the addition of any ligand.
Compared with the prior art, the invention has the following beneficial technical effects: the invention uses simple and commercialized double halogen, alkyne and 2-naphthol compound as raw materials to construct spiro [4.5] ring compound through [2+2+1] domino coupling reaction. Compared with other spiro cyclization reactions, the method has the following advantages: three simple raw materials are adopted, so that the challenge of difficult substrate synthesis in the traditional method is avoided; under the simplest condition, only a transition metal palladium catalyst is added, and no additional oxidant or ligand is needed, so that the reaction cost is reduced; the method has the advantages of wide substrate application range, mild reaction conditions, high conversion rate, high yield, good purity of the prepared product and wide industrial production prospect, and provides a new method for the fields of medicines, natural product synthesis, luminescent materials and the like.
Drawings
FIG. 1 is a graph of the UV absorption spectra of three compounds;
FIG. 2 shows fluorescence emission spectra of three compounds.
Detailed Description
Embodiments of the invention are described in further detail below:
Figure DEST_PATH_IMAGE003
Figure DEST_PATH_IMAGE004
in the above list, X, X ʹ is the halogen in the double halide, R is the substituent on the double halide, each R group corresponds to one double halide (1 a-1 o), and then under this technique, spiro compounds 4a-4j with the corresponding substituent R are obtained.
Under the condition of argon, 0.02 mmol of palladium acetate, 0.3 mmol of double halogenated matters 1 with different substituents R, 0.3 mmol of diphenylacetylene reactant 2a, 0.3 mmol of 2-naphthol reactant 3a, 0.4 mmol of potassium phosphate and 2.0 mL of 1, 4-dioxane are added into the reaction system in sequence, and then the mixture is heated to 130 ℃ in an oil bath for reaction for 16 hours.
Example 1:
Figure DEST_PATH_IMAGE005
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Diphenyl-2'H-spiro [ indene-1,1' -naphthalen]-2' -one (4 a). And (3) product data characterization: white solid (71.4 mg, yield: 90%), melting range: 176-.1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 9.9 Hz, 1H), 7.56-7.50 (m, 2H), 7.50-7.35 (m, 4H), 7.31-7.21 (m, 4H), 7.17 (t, J = 7.6 Hz, 1H), 7.09-7.03 (m, 1H), 7.02-6.94 (m, 4H), 6.86-6.81 (m, 2H), 6.40 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 197.1, 148.0, 146.6, 145.6, 145.2, 144.9, 141.3, 135.4, 134.5, 130.9, 130.2, 129.9, 129.8, 129.3, 129.1, 128.3, 128.2, 128.1, 127.8, 127.3, 127.1, 126.8, 126.6, 122.1, 121.9, 71.9. IR: 3059, 1663, 1598, 1562, 758, 699 cm-1. HRMS (ESI) m/z calculated for C30H20ONa [M+Na]+ 419.1412, found 419.1413。
The yield was 78% when 1, 2-diiodobenzene was chosen, 47% when 1-chloro-2-iodobenzene was chosen, and 43% when 1, 2-dibromobenzene was chosen; when 1-chloro-2-bromobenzene was used, the yield was 40%.
Example 2:
Figure DEST_PATH_IMAGE006
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1b, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 6-Methoxy-2,3-diphenyl-2'H-spiro [ indole-1, 1' -naphthalene]-2' -one (4 b). And (3) product data characterization: white solid (67.4 mg, yield: 79%). melting range: 238-.1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 9.9 Hz, 1H), 7.53-7.50 (m, 2H), 7.46-7.35 (m, 4H), 7.30-7.24 (m, 2H), 7.21-7.15 (m, 2H), 7.00-6.94 (m, 3H), 6.82-6.75 (m, 3H), 6.58 (d, J = 2.3 Hz, 1H), 6.39 (d, J = 9.9 Hz, 1H), 3.69 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 197.1, 158.9, 149.5, 146.5, 144.5, 143.3, 141.5, 138.5, 135.6, 134.7, 131.0, 130.2, 129.8, 129.7, 129.1, 129.0, 128.1, 128.0, 127.8, 127.2, 127.0, 126.7, 122.6, 112.7, 109.0, 71.6, 55.7. IR (KBr): 3053, 2934, 1664, 1597, 1482, 1306, 1280, 912, 742 cm-1. HRMS (ESI) m/z calculated for C31H22O2Na [M+Na]+ 449.1517, found 449.1519。
Example 3:
Figure DEST_PATH_IMAGE007
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1c, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 6-Chloro-2, 3-diphenylene-2 'H-spiro [ indole-1, 1' -naphthalen]-2' -one (4 c). And (3) product data characterization: yellow solid (63.8 mg, yield: 74%). melting range: 252-.1H NMR (400 MHz, CDCl3): δ 7.57 (d, J = 9.9 Hz, 1H), 7.43-7.27 (m, 6H), 7.21-7.16 (m, 1H), 7.15-7.06 (m, 3H), 6.93-6.84 (m, 5H), 6.73 (dd, J = 7.9, 1.4 Hz, 2H), 6.30 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 196.0, 149.1, 146.5, 145.7, 144.2, 143.9, 140.3, 134.8, 134.1, 132.0, 130.9, 130.3, 129.7, 129.5, 129.2, 129.0, 128.2, 128.1, 128.0, 127.9, 127.4, 127.0, 126.5, 122.8, 122.3, 71.5. IR (KBr): 3057, 2924, 1665, 1589, 1453, 1233, 1200, 827, 741, 698 cm-1. HRMS (ESI) m/z calculated for C30H19ClONa [M+Na]+ 453.1022, found 453.1023。
Example 4:
Figure DEST_PATH_IMAGE008
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1d, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, the reaction solution is directly usedSpin drying, and separating by column chromatography to obtain target product 2,3-Diphenyl-6- (trifluoromethyl) -2'H-spiro [ indene-1,1' -naphthalene]-2' -one (4 d). And (3) product data characterization: white solid (67.3 mg, yield: 70%). melting range 203-204 ℃.1H NMR (400 MHz, CDCl3): δ 7.69 (d, J = 9.9 Hz, 1H), 7.56-7.37 (m, 6H), 7.35-7.25 (m, 2H), 7.20 (t, J = 7.5 Hz, 1H), 7.11 (d, J = 8.3 Hz, 1H), 7.05-6.93 (m, 4H), 6.88-6.81 (m, 3H), 6.41 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 195.9, 149.1, 147.7, 147.6, 146.6, 146.4, 144.3, 143.7, 140.1, 134.8, 134.0, 131.0, 130.3, 129.7, 129.5, 129.2, 129.1, 128.2, 128.1, 127.5, 127.1, 126.5, 122.6, 120.6, 120.4 (q, J = 257.2 Hz), 115.3, 71.6. 19F NMR (376 MHz, CDCl3): δ -57.88. IR (KBr): 3058, 2924, 1667, 1604, 1476, 1259, 1221, 1166, 750, 698 cm-1. HRMS (ESI) m/z calculated for C31H19F3O2Na [M+Na]+503.1235, found 503.1236。
Example 5:
Figure DEST_PATH_IMAGE009
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1e, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, the reaction solution is directly dried in a spinning mode, and a target product Methyl 2' -oxo-2,3-diphenyl-2' H-spiro [ indole-1, 1' -naphthalene ] -6-carboxlate (4e) is obtained through column chromatography separation.
And (3) product data characterization: yellow solid (76.4 mg, yield: 84%). melting range: 258-.1H NMR (400 MHz, CDCl3): δ 7.91 (d, J = 8.0 Hz, 1H), 7.64 (d, J = 9.9 Hz, 1H), 7.58 (s, 1H), 7.49-7.34 (m, 6H), 7.31-7.19 (m, 2H), 7.11 (t, J = 7.6 Hz, 1H), 7.03-6.90 (m, 3H), 6.86 (d, J = 7.7 Hz, 1H), 6.79 (d, J = 7.5 Hz, 2H), 6.35 (d, J = 9.9 Hz, 1H), 3.76 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 196.0, 167.0, 150.5, 148.7, 147.9, 146.7, 144.2, 140.1, 134.7, 134.0, 130.9, 130.4, 130.0, 129.9, 129.6, 129.3, 129.1, 128.3, 128.2, 128.0, 127.7, 127.0, 126.6, 122.9, 121.6, 71.6, 52.1. IR (KBr): 3057, 2924, 1718, 1665, 1603, 1439, 1285, 1233, 1117, 758, 698 cm-1. HRMS (ESI) m/z calculated for C32H22O3Na [M+Na]+ 477.1467, found 477.1468。
Example 6:
Figure DEST_PATH_IMAGE010
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1f, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2' -Oxo-2,3-diphenyl-2' H-spiro [ indene-1,1' -naphthalene]-6-carbonitrile (4 f). And (3) product data characterization: white solid (56.5 mg, yield: 67%). melting range 272-.1H NMR (400 MHz, CDCl3): δ 7.73 (d, J = 9.9 Hz, 1H), 7.56-7.42 (m, 6H), 7.38-7.31 (m, 2H), 7.27-7.18 (m, 3H), 7.09-6.98 (m, 3H), 6.92-6.82 (m, 3H), 6.42 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 195.2, 150.2, 148.9, 147.9, 146.8, 143.8, 139.3, 134.0, 133.3, 132.4, 131.0, 130.5, 129.6, 129.4, 129.2, 129.1, 128.5, 128.4, 128.2, 127.9, 126.7, 126.3, 125.1, 122.3, 119.2, 109.1, 71.5. IR (KBr): 3057, 2224, 1664, 1596, 1563, 1477, 1433, 1267, 1234, 1200, 839, 740, 700 cm-1. HRMS (ESI) m/z calculated for C31H19NONa [M+Na]+444.1364, found 444.1369。
Example 7:
Figure DEST_PATH_IMAGE011
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1g, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 5-Methoxy-2,3-diphenyl-2'H-spiro [ indole-1, 1' -naphthalene]-2' -one (4 g). And (3) product data characterization: yellow solid (69.1 mg, yield: 81%). melting range: 79-80 ℃.1H NMR (400 MHz, CDCl3): δ 7.57 (d, J = 9.9 Hz, 1H), 7.46-7.41 (m, 2H), 7.39-7.29 (m, 4H), 7.25-7.15 (m, 1H), 7.11-7.06 (m, 1H), 6.94-6.85 (m, 4H), 6.82 (d, J = 8.3 Hz, 1H), 6.76-6.70 (m, 3H), 6.52 (dd, J = 8.3, 2.4 Hz, 1H), 6.30 (d, J = 9.9 Hz, 1H), 3.64 (s, 3H)。
Example 8:
Figure DEST_PATH_IMAGE012
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant for 1h, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 5-Fluoro-2, 3-diphenylene-2 'H-spiro [ indole-1, 1' -naphthalen]-2' -one (4 h). And (3) product data characterization: yellow solid (62.2 mg, yield: 75%). melting range 89-90 ℃.1H NMR (400 MHz, CDCl3): δ 7.66 (d, J = 9.9 Hz, 1H), 7.53-7.39 (m, 6H), 7.32-7.26 (m, 1H), 7.22-7.16 (m, 1H), 7.05-6.91 (m, 6H), 6.86-6.81 (m, 2H), 6.79-6.72 (m, 1H), 6.39 (d, J = 9.9 Hz, 1H)。
Example 9:
Figure DEST_PATH_IMAGE013
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1i, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, the reaction liquid is directly dried in a spinning way, and a target product Methyl 2' -oxo-2,3-diphenyl-2' H-spiro [ indole-1, 1' -naphthalene ] is obtained by column chromatography separation]-5-carboxylate (4 i). And (3) product data characterization: yellow solid (62.7 mg, yield: 69%). melting range 277-278 ℃.1H NMR (400 MHz, CDCl3): δ 7.94 (s, 1H), 7.79 (dd, J = 7.9, 1.2 Hz, 1H), 7.69 (d, J = 9.9 Hz, 1H), 7.56-7.39 (m, 6H), 7.30 (t, J = 7.2 Hz, 1H), 7.19 (t, J= 7.3 Hz, 1H), 7.10-6.92 (m, 5H), 6.84 (d, J = 6.9 Hz, 2H), 6.41 (d, J = 9.9 Hz, 1H), 3.86 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 195.9, 167.1, 152.5, 146.5, 146.4, 146.1, 144.2, 140.2, 134.7, 134.1, 130.9, 130.3, 130.1, 129.8, 129.6, 129.2, 129.1, 128.3, 128.2, 128.1, 128.0, 127.5, 127.0, 126.6, 122.9, 121.8, 71.8, 52.2. IR (KBr): 3057, 2951, 1720, 1665, 1437, 1286, 1242, 1199, 1099, 742, 699 cm-1. HRMS (ESI) m/z calculated for C32H22O3Na [M+Na]+ 477.1467, found 477.1467。
Example 10:
Figure DEST_PATH_IMAGE014
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1j, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, the reaction liquid is directly dried in a rotating way, and a target product 4-Fluoro-2, 3-diphenylyl-2' H-spiro [2 ] is obtained by column chromatography separationindene-1,1'-naphthalen]-2' -one (4 j). And (3) product data characterization: white solid (43.1 mg, yield: 52%). melting range: 232-.1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 9.9 Hz, 1H), 7.55-7.51 (m, 2H), 7.44-7.35 (m, 4H), 7.32-7.27 (m, 1H), 7.24-7.19 (m, 1H), 7.06-6.90 (m, 6H), 6.82-6.74 (m, 3H), 6.38 (d, J = 9.9 Hz, 1H)。
Figure DEST_PATH_IMAGE015
Figure DEST_PATH_IMAGE016
In the above list, R1、R2Each row R being a substituent carried at both ends of an alkyne1、R2The radical corresponds to an alkyne (2 b-2 l), and then, under this technique, the corresponding substituent R is obtained1、R2The spiro compound 4a '-4 j'.
Under the condition of argon, 0.02 mmol of palladium acetate, 0.3 mmol of 1-bromo-2-iodobenzene 1a, 0.3 mmol of alkyne 2, 0.3 mmol of 2-naphthol 3a, 0.4 mmol of potassium phosphate and 2.0 mL of 1, 4-dioxane are sequentially added into the reaction system, and then the mixture is heated to 130 ℃ in an oil bath for reaction for 16 hours.
Example 11:
Figure DEST_PATH_IMAGE017
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 1,1'- ((2' -Oxo-2'H-spiro [ indene-1,1' -naphthalene)]-2,3-diyl) bis (4,1-phenylene)) bis (ethane-1-one) (4 a'). And (3) product data characterization: yellow solid (72.1 m)g, yield: 75%), melting range 117-118 deg.C.1H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 8.3 Hz, 2H), 7.71 (d, J = 9.9 Hz, 1H), 7.61 (dd, J = 18.8, 8.4 Hz, 4H), 7.46 (d, J = 7.5 Hz, 1H), 7.33-7.26 (m, 3H), 7.21-7.16 (m, 1H), 7.15-7.08 (m, 1H), 7.04 (d, J = 7.5 Hz, 1H), 6.93-6.88 (m, 3H), 6.41 (d, J = 9.9 Hz, 1H), 2.67 (s, 3H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 197.8, 197.5, 196.1, 147.9, 146.6, 145.9, 145.2, 144.4, 140.3, 140.0, 139.0, 136.9, 135.7, 131.0, 130.4, 129.9, 129.8, 129.3, 129.2, 128.3, 128.2, 128.1, 127.3, 127.0, 126.6, 122.2, 122.1, 72.0, 26.8, 26.6. IR (KBr): 3060, 2923, 1680, 1603, 1401, 1358, 1268, 1192, 824, 755 cm-1. HRMS (ESI) m/z calculated for C34H24O3Na [M+Na]+ 503.1623, found 503.1621。
Example 12:
Figure DEST_PATH_IMAGE018
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2c, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product Diethyl 4,4'- (2' -oxo-2'H-spiro [ indene-1,1' -naphthalene)]-2,3-diyl) dibenzoate (4 b'). And (3) product data characterization: white solid (96.2 mg, yield: 89%). melting range: 142-.1H NMR (400 MHz, CDCl3): δ 8.16 (d, J = 8.1 Hz, 2H), 7.76-7.57 (m, 5H), 7.46 (d, J = 7.5 Hz, 1H), 7.37-7.26 (m, 3H), 7.22-7.03 (m, 3H), 6.92 (t, J = 8.8 Hz, 3H), 6.42 (d, J = 9.9 Hz, 1H), 4.44 (q, J = 7.0 Hz, 2H), 4.28 (q, J = 7.0 Hz, 2H), 1.44 (t, J = 7.1 Hz, 3H), 1.31 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 196.1, 166.4, 166.2, 147.9, 146.5, 145.7, 145.3, 144.5, 140.3, 139.6, 138.7, 130.9, 130.4, 130.3, 129.8, 129.6, 129.4, 129.0, 128.1, 128.0, 127.2, 127.0, 126.5, 122.1, 122.0, 72.0, 61.2, 60.9, 14.5, 14.4. IR (KBr): 3061, 2983, 1716, 1666, 1607, 1275, 1180, 1107, 1021, 757 cm-1. HRMS (ESI) m/z calculated for C36H28O5Na [M+Na]+ 563.1834, found 563.1833。
Example 13:
Figure DEST_PATH_IMAGE019
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2d, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Bis (3-chlorophenylyl) -2'H-spiro [ indole-1, 1' -naphthalen]-2'-one (4 c'). And (3) product data characterization: white solid (75.4 mg, yield: 81%). melting range: 92-93 ℃.1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 9.9 Hz, 1H), 7.51 (s, 1H), 7.43-7.32 (m, 4H), 7.29-7.20 (m, 3H), 7.18-7.12 (m, 1H), 7.09-7.04 (m, 1H), 7.00-6.97 (m, 2H), 6.94-6.85 (m, 2H), 6.79 (t, J = 1.8 Hz, 1H), 6.71-6.67 (m, 1H), 6.36 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 196.2, 147.8, 146.5, 144.6, 144.5, 140.3, 136.5, 136.0, 134.9, 134.0, 130.9, 130.4, 130.3, 129.8, 129.4, 129.3, 128.9, 128.5, 128.1, 128.0, 127.9, 127.6, 127.5, 127.1, 127.0, 126.5, 122.0, 121.9, 71.9. IR (KBr): 3061, 2924, 1638, 1592, 1562, 1461, 1394, 1270, 1209, 752 cm-1. HRMS (ESI) m/z calculated for C30H18Cl2ONa [M+Na]+ 487.0632, found 487.0635。
Example 14:
Figure DEST_PATH_IMAGE020
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2e, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Bis (2-fluorophenyl) -2'H-spiro [ indole-1, 1' -naphthalen]-2'-one (4 d'). And (3) product data characterization: white solid (67.5 mg, yield: 78%). melting range 70-71 ℃.1H NMR (400 MHz, CDCl3): δ 7.56 (d, J = 9.8 Hz, 1H), 7.36-6.92 (m, 14H), 6.83 (t, J = 7.3 Hz, 1H), 6.74 (t, J = 9.4 Hz, 1H), 6.38 (d, J = 9.9 Hz, 1H)。
Example 15:
Figure DEST_PATH_IMAGE021
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2f, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Di (thiophen-2-yl) -2'H-spiro [ indole-1, 1' -naphthalen]-2'-one (4 e'). And (3) product data characterization: yellow solid (31.9 mg, yield: 39%). melting range 82-83 ℃.1H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 9.9 Hz, 1H), 7.58 (d, J = 5.1 Hz, 1H), 7.48 (d, J = 7.1 Hz, 1H), 7.37-7.15 (m, 6H), 7.07-6.93 (m, 4H), 6.72 (dd, J = 5.0, 3.9 Hz, 1H), 6.46-6.41 (m, 2H)。
Example 16:
Figure DEST_PATH_IMAGE022
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2g, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Dipropyl-2'H-spiro [ indene-1,1' -naphthalen]-2'-one (4 f'). And (3) product data characterization: yellow solid (62.4 mg, yield: 95%). melting range: 88-89 ℃.1H NMR (400 MHz, CDCl3): δ 7.63 (d, J = 9.9 Hz, 1H), 7.40 (dd, J = 7.6, 1.1 Hz, 1H), 7.31-7.21 (m, 3H), 7.18-7.12 (m, 1H), 7.01-6.94 (m, 1H), 6.83 (d, J = 7.4 Hz, 1H), 6.65 (d, J = 7.8 Hz, 1H), 6.35 (d, J = 9.9 Hz, 1H), 2.63 (t, J = 7.6 Hz, 2H), 2.29-2.20 (m, 1H), 2.09-1.99 (m, 1H), 1.82-1.65 (m, 2H), 1.20-1.09 (m, 2H), 1.05 (t, J= 7.4 Hz, 3H), 0.76 (t, J = 7.3 Hz, 3H)。
Example 17:
Figure DEST_PATH_IMAGE023
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2h, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Bis (tert-butylmethylicilyl) oxy) -2'H-spiro [ indole-1, 1' -naphthalene]-2'-one (4 g'). And (3) product data characterization: white solid (92.7 mg, yield: 87%). melting range: 196-197 ℃.1H NMR (400 MHz, CDCl3): δ 7.57 (d, J = 9.9 Hz, 1H), 7.38 (dd, J = 10.9, 7.9 Hz, 2H), 7.25-7.09 (m, 3H), 6.96 (t, J = 7.4 Hz, 1H), 6.88 (d, J = 7.4 Hz, 1H), 6.78 (d, J = 7.7 Hz, 1H), 6.31 (d, J = 9.9 Hz, 1H), 4.83 (s, 2H), 4.70 (d, J = 14.4 Hz, 1H), 4.48 (d, J = 14.4 Hz, 1H), 0.94 (s, 9H), 0.66 (s, 9H), 0.16 (s, 6H), -0.24 (d, J = 15.3 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ 196.3, 147.9, 147.1, 145.4, 144.5, 141.2, 140.2, 130.1, 129.8, 129.6, 127.4, 127.1, 126.9, 126.4, 125.7, 121.4, 121.1, 69.9, 59.0, 58.4, 26.1, 25.9, 18.5, 18.4, -5.1, -5.2, -5.8, -5.9. IR (KBr): 3059, 2946, 2857, 1660, 1462, 1398, 1252, 1080, 838, 762 cm-1. HRMS (ESI) m/z calculated for C32H44O3Si2Na [M+Na]+555.2727, found 555.2730。
Example 18:
Figure DEST_PATH_IMAGE024
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2i, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 3-Phenyl-2- (trimethylsilyl) -2'H-spiro [ indene-1,1' -naphthalen]-2'-one (4 h'). And (3) product data characterization: yellow solid (49.5 mg, yield: 63%). melting range: 155-156 ℃.1H NMR (400 MHz, CDCl3): δ 7.67 (d, J = 9.9 Hz, 1H), 7.57-7.41 (m, 6H), 7.30 (t, J = 7.4 Hz, 1H), 7.22 (t, J = 7.1 Hz, 1H), 7.19-7.13 (m, 1H), 7.02-6.96 (m, 4H), 6.41 (d, J = 9.9 Hz, 1H), -0.23 (s, 9H). 13C NMR (100 MHz, CDCl3): δ 197.6, 159.2, 149.8, 148.3, 146.3, 145.9, 141.4, 136.9, 130.3, 130.1, 129.7, 129.4, 128.4, 128.0, 127.7, 127.6, 127.1, 126.7, 126.3, 121.7, 121.2, 74.0, 0.3. IR (KBr): 3062, 2957, 1663, 1558, 1451, 1395, 1243, 1202, 859, 749, 700 cm-1. HRMS (ESI) m/z calculated for C27H24OSiNa [M+Na]+ 415.1494, found 415.1499。
Example 19:
Figure DEST_PATH_IMAGE025
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2j, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 3-Phenyl-2- (triethylsilyl) -2'H-spiro [ indene-1,1' -naphthalen]-2'-one (4 i'). And (3) product data characterization: yellow solid (51.3 mg, yield: 59%). melting range: 87-88 ℃.1H NMR (400 MHz, CDCl3): δ 7.68 (d, J = 9.9 Hz, 1H), 7.57-7.42 (m, 6H), 7.32-7.28 (m, 1H), 7.21 (m, 1H), 7.17-7.12 (m, 1H), 7.02-6.87 (m, 4H), 6.42 (d, J = 9.9 Hz, 1H), 0.70 (t, J = 7.9 Hz, 9H), 0.39-0.12 (m, 6H). 13C NMR (100 MHz, CDCl3): δ 196.9, 159.7, 150.7, 147.2, 146.4, 145.9, 141.3, 137.0, 130.2, 130.0, 129.7, 129.3, 128.3, 128.0, 127.7, 127.6, 127.3, 127.1, 126.4, 121.7, 121.2, 73.8, 7.6, 4.4. IR (KBr): 3061, 2953, 2877, 1662, 1455, 1234, 1201, 1013, 737, 702 cm-1. HRMS (ESI) m/z calculated for C30H30OSiNa [M+Na]+ 457.1964, found 457.1964。
Example 20:
Figure DEST_PATH_IMAGE026
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2k, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2- (2- ((Tert-butylmethylisolyl) oxy) ethyl) -3-ethyl-2'H-spiro [ indole-1, 1' -naphthalen]-2'-one (4j' -1) and 3- (2- ((Tert-butylmethylistyl) oxy) ethyl) -2-ethyl-2'H-spiro [ indole-1, 1' -naphthalene]A total of 70.6 mg of (E) -2'-one (4j' -2). Product 4r' -1 data characterization: a white solid. Melting range 107-108 ℃.1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 9.9 Hz, 1H), 7.40 (dd, J = 7.6, 1.0 Hz, 1H), 7.34-7.23 (m, 3H), 7.19-7.13 (m, 1H), 7.05-6.96 (m, 1H), 6.86 (d, J = 7.4 Hz, 1H), 6.64 (d, J = 7.7 Hz, 1H), 6.35 (d, J = 9.9 Hz, 1H), 3.42-3.22 (m, 2H), 2.68 (q, J = 7.6 Hz, 2H), 2.52-2.33 (m, 2H), 1.29 (t, J = 7.6 Hz, 3H), 0.80 (s, 9H), -0.09 (d, J = 3.8 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ 197.9, 148.9, 146.1, 145.8, 145.7, 142.2, 140.8, 130.4, 130.2, 129.8, 127.7, 127.6, 127.4, 127.0, 125.7, 122.0, 119.9, 71.2, 62.2, 31.5, 26.1, 19.2, 18.4, 13.9, -5.2. IR (KBr): 3061, 2957, 2863, 1658, 1462, 1394, 1243, 1086, 834, 749 cm-1. HRMS (ESI) m/z calculated for C28H35O2Si [M+H]+431.2406, found 431.2405. data characterization of product 4r' -2: white solid.1H NMR (600 MHz, CDCl3): δ 7.64 (d, J = 9.9 Hz, 1H), 7.40 (d, J = 7.5 Hz, 1H), 7.32-7.21 (m, 3H), 7.16-7.13 (m, 1H), 6.97 (t, J = 7.4 Hz, 1H), 6.84 (d, J = 7.4 Hz, 1H), 6.69 (d, J = 7.8 Hz, 1H), 6.36 (d, J = 9.9 Hz, 1H), 3.90 (t, J = 7.3 Hz, 2H), 2.98-2.85 (m, 2H), 2.44-2.36 (m, 1H), 2.19-2.12 (m, 1H), 0.91 (s, 9H), 0.79 (t, J = 7.7 Hz, 3H), 0.09 (d, J = 3.5 Hz, 6H). 13C NMR (100 MHz, CDCl3): δ 197.9, 150.1, 148.6, 146.3, 146.0, 141.0, 138.7, 130.3, 130.1, 129.7, 127.6, 127.5, 127.4, 126.9, 125.4, 121.7, 119.8, 71.2, 62.2, 29.9, 26.1, 20.6, 18.5, 13.8, -5.1. IR (KBr): 3061, 2927, 1723, 1658, 1459, 1391, 1236, 1204, 1046, 823, 750 cm-1. HRMS (ESI) m/z calculated for C28H34O2SiNa [M+Na]+ 453.2226, found 453.2227。
Example 21:
Figure DEST_PATH_IMAGE027
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2l, 0.3 mmol of reactant 3a, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, the reaction liquid is directly dried in a spinning way, and the target product 3-Ethyl-2- (prop-1-en-2-yl) -2'H-spiro [ indole-1, 1' -naphthalen ] is obtained by separating with a column chromatography method]-2'-one (4 k'). And (3) product data characterization: yellow solid (33.7 mg, yield: 54%). melting range: 62-63 ℃.1H NMR (400 MHz, CDCl3): δ 7.61 (d, J = 9.9 Hz, 1H), 7.38 (d, J = 6.9 Hz, 1H), 7.30-7.11 (m, 4H), 7.01-6.91 (td, J = 7.3, 1.4 Hz, 1H), 6.83 (d, J = 7.5 Hz, 1H), 6.68 (d, J = 7.6 Hz, 1H), 6.34 (d, J = 9.9 Hz, 1H), 5.39-5.29 (m, 1H), 5.16-5.06 (m, 1H), 2.38-2.27 (m, 1H), 2.22-2.02 (m, 4H), 0.77 (t, J = 7.6 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 197.5, 148.6, 148.5, 145.9, 145.8, 145.2, 140.9, 139.3, 130.4, 130.2, 129.8, 127.7, 127.6, 127.4, 126.9, 125.5, 121.9, 120.6, 116.4, 71.0, 23.1, 21.1, 13.8. IR (KBr): 3066, 2969, 1662, 1457, 1385, 1269, 1233, 1203, 903, 818, 755 cm-1. HRMS (ESI) m/z calculated for C23H21O [M+H]+313.1592, found 313.1594。
Figure DEST_PATH_IMAGE028
Figure DEST_PATH_IMAGE029
The above list is the application of different 2-naphthols to this technique, in which R ' is a substituent carried on 2-naphthol, each R ' group corresponding to one 2-naphthol (3 b-3 n), and then in which the spiro compound 4a "-4 m" carrying the corresponding substituent R ' is obtained.
Under the condition of argon, 0.02 mmol of palladium acetate, 0.3 mmol of 1-bromo-2-iodobenzene 1a, 0.3 mmol of tolane 2a, 0.3 mmol of 2-naphthol compound 3, 0.4 mmol of potassium phosphate and 2.0 mL of 1, 4-dioxane are sequentially added into the reaction system, and then the mixture is heated to 130 ℃ in an oil bath for reaction for 16 hours.
Example 22:
Figure DEST_PATH_IMAGE030
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1b, 0.3 mmol of reactant 2a, 0.3 mmol of reactant 3b, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 6' -Chloro-2, 3-diphenylene-2 ' H-spiro [ indole-1, 1' -naphthalen]-2' -one (4a ʹ ʹ). And (3) product data characterization: white solid (70.7 mg, yield: 82%). melting range 122-123 ℃.1H NMR (400 MHz, CDCl3): δ 7.62 (d, J = 10.0 Hz, 1H), 7.55 (d, J = 7.2 Hz, 2H), 7.52-7.39 (m, 4H), 7.34-7.28 (m, 2H), 7.19-6.99 (m, 6H), 6.96-6.83 (m, 3H), 6.47 (d, J= 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 196.1, 147.3, 145.5, 145.1, 144.8, 144.6, 139.5, 135.0, 134.2, 133.4, 131.4, 130.6, 129.6, 129.5, 129.1, 129.0, 128.5, 128.2, 128.1, 128.0, 127.9, 127.3, 126.6, 122.1, 121.7, 71.4. IR (KBr): 3059, 2923, 1666, 1486, 1452, 1231, 1196, 881, 749, 697 cm-1. HRMS (ESI) m/z calculated for C30H19ClONa [M+Na]+ 453.1022, found 453.1022。
Example 23:
Figure DEST_PATH_IMAGE031
to a 5.0 mL sealed tube were added, under argon, 0.02 mmol of palladium acetate, 0.3 mmol of the reactant 1a, 0.3 mmol of the reactant 2b, 0.3 mmol of the reactant 3c, 0.4 mmol of potassium phosphate, and 2.0 mmol of potassium phosphate in that ordermL of 1, 4-dioxane, then heated to 130 ℃ in an oil bath, and reacted for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 6' -Bromo-2, 3-diphenylene-2 ' H-spiro [ indene-1,1' -naphthalene]-2' -one (4b ʹ ʹ). And (3) product data characterization: yellow solid (75.1 mg, yield: 79%). melting range: 124-.1H NMR (400 MHz, CDCl3): δ 7.64-7.59 (m, 2H), 7.55 (d, J = 6.9 Hz, 2H), 7.51-7.39 (m, 3H), 7.35-7.24 (m, 3H), 7.12-7.01 (m, 5H), 6.91-6.81 (m, 3H), 6.47 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 196.0, 147.1, 145.4, 145.1, 144.7, 144.6, 140.0, 135.0, 134.1, 133.5, 132.5, 131.6, 129.6, 129.1, 129.0, 128.7, 128.2, 128.1, 128.0, 127.8, 127.3, 126.6, 122.2, 121.7, 121.3, 71.4. IR (KBr): 3058, 2923, 1666, 1485, 1452, 1270, 1231, 1194, 748, 698 cm-1. HRMS (ESI) m/z calculated for C30H19BrONa [M+Na]+ 497.0517, found 497.0517.
Example 24:
Figure DEST_PATH_IMAGE032
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3d, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, the reaction liquid is directly dried in a spinning way, and a target product of Ethyl 2' -oxo-2,3-diphenyl-2' H-spiro [ indole-1, 1' -naphthalene ] is obtained by column chromatography separation]-6' -carboxylate (4c ʹ ʹ). And (3) product data characterization: yellow solid (73.1 mg, yield: 78%). melting range: 130-.1H NMR (400 MHz, CDCl3): δ 8.01 (s, 1H), 7.71 (d, J = 8.1 Hz, 1H), 7.62 (d, J = 10.0 Hz, 1H), 7.46-7.39 (m, 2H), 7.37-7.26 (m, 3H), 7.23-7.08 (m, 2H), 6.98-6.83 (m, 6H), 6.77-6.68 (m, 2H), 6.36 (d, J = 9.9 Hz, 1H), 4.25 (q, J = 7.1 Hz, 2H), 1.25 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 195.9, 165.7, 147.1, 146.2, 145.6, 145.3, 145.2, 144.7, 135.0, 134.2, 131.4, 131.1, 130.1, 129.9, 129.6, 129.1, 129.0, 128.2, 128.1, 127.5, 127.3, 127.2, 126.6, 122.2, 121.7, 71.9, 61.3, 14.4. IR (KBr): 3059, 2983, 1717, 1668, 1453, 1373, 1285, 1222, 1114, 1022, 756, 698 cm-1. HRMS (ESI) m/z calculated for C33H24O3Na [M+Na]+ 491.1623, found 491.1623。
Example 25:
Figure DEST_PATH_IMAGE033
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3e, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 6' -Acetyl-2, 3-diphenylene-2 ' H-spiro [ indene-1,1' -naphthalene]-2' -one (4d ʹ ʹ). And (3) product data characterization: yellow solid (66.7 mg, yield: 76%). melting range: 132-.1H NMR (400 MHz, CDCl3): δ 7.91 (d, J = 1.5 Hz, 1H), 7.66-7.57 (m, 2H), 7.41 (d, J = 7.0 Hz, 2H), 7.38-7.25 (m, 3H), 7.22-7.10 (m, 2H), 6.99-6.81 (m, 6H), 6.72 (dd, J = 7.9, 1.5 Hz, 2H), 6.36 (d, J = 9.9 Hz, 1H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 197.0, 195.8, 147.0, 146.5, 145.6, 145.4, 145.3, 144.6, 136.6, 135.0, 134.1, 130.4, 130.1, 129.7, 129.6, 129.1, 129.0, 128.3, 128.2, 128.1, 127.7, 127.4, 127.3, 126.6, 122.2, 121.7, 71.8, 26.6. IR (KBr): 3058, 2923, 1681, 1618, 1453, 1374, 1273, 1222, 756, 697 cm-1. HRMS (ESI) m/z calculated for C32H22O2Na [M+Na]+ 461.1517, found 461.1513。
Example 26:
Figure DEST_PATH_IMAGE034
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3f, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2' -Oxo-2,3-diphenyl-2' H-spiro [ indene-1,1' -naphthalene]-6' -carbonitrile (4e ʹ ʹ). And (3) product data characterization: white solid (59.9 mg, yield: 71%). melting range: 146-147 ℃.1H NMR (400 MHz, CDCl3): δ 7.59 (d, J = 1.5 Hz, 1H), 7.53 (d, J = 10.0 Hz, 1H), 7.45-7.24 (m, 6H), 7.23-7.11 (m, 2H), 7.00-6.83 (m, 6H), 6.74-6.63 (m, 2H), 6.41 (d, J = 10.0 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 195.1, 146.5, 146.4, 145.6, 145.5, 144.2, 143.7, 134.7, 133.9, 133.5, 133.2, 130.8, 129.5, 129.1, 129.0, 128.7, 128.5, 128.3, 128.2, 128.0, 127.5, 126.8, 122.4, 121.7, 118.0, 111.9, 71.7. IR (KBr): 3059, 2923, 2230, 1668, 1623, 1451, 1265, 1210, 754, 695 cm-1. HRMS (ESI) m/z calculated for C31H19NONa [M+Na]+ 444.1364, found 444.1364。
Example 27:
Figure DEST_PATH_IMAGE035
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of the reactant 1a, 0.3 mmol of the reactant 2b, 0.3 mmol of the reactant 3g, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 6' -Methoxy-2,3-diphenyl-2' H-spiro [ indole-1, 1' -naphthalene]-2' -one (4f ʹ ʹ). And (3) product data characterization: yellow solid (67.4 mg, yield: 79%). melting range 115 ℃ and 116 ℃.1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 9.9 Hz, 1H), 7.55 (d, J = 7.3 Hz, 2H), 7.51-7.38 (m, 3H), 7.37-7.21 (m, 2H), 7.16-6.99 (m, 5H), 6.96 (d, J = 2.4 Hz, 1H), 6.89 (t, J = 6.9 Hz, 3H), 6.76 (dd, J = 8.6, 2.5 Hz, 1H), 6.43 (d, J = 9.9 Hz, 1H), 3.82 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 197.1, 158.9, 148.1, 146.1, 145.5, 145.3, 144.6, 135.3, 134.5, 132.8, 130.8, 129.6, 129.2, 128.9, 128.3, 128.0, 127.9, 127.8, 127.2, 127.1, 126.4, 121.9, 121.8, 116.8, 114.6, 71.3, 55.5. IR (KBr): 3059, 2931, 1662, 1563, 1495, 1455, 1269, 1167, 1034, 742, 698 cm-1. HRMS (ESI) m/z calculated for C31H22O2Na [M+Na]+ 449.1517, found 449.1517。
Example 28:
Figure DEST_PATH_IMAGE036
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3h, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain a target product 6' - ((Tert-butylmethylicilyl) oxy) -2, 3-diphenylyl-2 ' H-spiro [ indole-1, 1' -naphthalene]-2' -one (4g ʹ ʹ). And (3) product data characterization: yellow solid (89.6 mg, yield: 85%). melting range 98-99 ℃.1H NMR (400 MHz, CDCl3): δ 7.58-7.50 (m, 3H), 7.46-7.36 (m, 3H), 7.32-7.22 (m, 2H), 7.08 (t, J = 7.5 Hz, 1H), 7.04-6.96 (m, 4H), 6.89 (d, J = 2.4 Hz, 1H), 6.87-6.76 (m, 3H), 6.67 (dd, J = 8.4, 2.4 Hz, 1H), 6.36 (d, J = 9.9 Hz, 1H), 0.98 (s, 9H), 0.20 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 197.2, 155.1, 148.2, 146.0, 145.6, 144.4, 135.3, 134.6, 133.4, 131.0, 129.7, 129.3, 128.9, 128.3, 128.0, 127.9, 127.8, 127.1, 127.0, 126.4, 122.6, 121.9, 121.8, 120.9, 71.5, 25.8, 18.3, -4.2, -4.3. IR (KBr): 3059, 2932, 2857, 1665, 1494, 1275, 1169, 973, 846, 751, 696 cm-1. HRMS (ESI) m/z calculated for C36H34O2SiNa [M+Na]+ 549.2226, found 549.2223。
Example 29:
Figure DEST_PATH_IMAGE037
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3i, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3,6' -Triphenyl-2' H-spiro [ indole-1, 1' -naphthalen]-2' -one (4h ʹ ʹ). And (3) product data characterization: yellow solid (73.7 mg, yield: 78%). melting range 141-142 ℃.1H NMR (400 MHz, CDCl3): δ 7.75 (d, J = 9.9 Hz, 1H), 7.65 (d, J = 1.4 Hz, 1H), 7.60-7.51 (m, 4H), 7.50-7.22 (m, 9H), 7.12-6.98 (m, 6H), 6.90 (dd, J = 7.5, 1.7 Hz, 2H), 6.46 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 196.7, 147.8, 146.2, 145.6, 145.2, 144.9, 140.6, 140.1, 139.9, 135.3, 134.5, 130.2, 129.7, 129.4, 129.3, 129.1, 129.0, 128.6, 128.1, 128.0, 127.9, 127.8, 127.5, 127.2, 127.1, 127.0, 126.5, 122.0, 121.8, 71.7. IR (KBr): 3058, 2923, 1664, 1487, 1452, 1267, 1226, 1186, 752, 698 cm-1. HRMS (ESI) m/z calculated for C36H24ONa [M+Na]+495.1725, found 495.1724。
Example 30:
Figure DEST_PATH_IMAGE038
under the condition of argon, 0.02 mmol of palladium acetate and 0.3 mm of palladium acetate are sequentially added into a 5.0 mL sealed tubeol reactant 1a, 0.3 mmol reactant 2b, 0.3 mmol reactant 3j, 0.4 mmol potassium phosphate, 2.0 mL 1, 4-dioxane, then heated to 130 ℃ in an oil bath for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Diphenyl-6' - (thiophen-2-yl) -2' H-spiro [ indene-1,1' -naphthalene]-2' -one (4i ʹ ʹ). And (3) product data characterization: yellow solid (67.0 mg, yield: 70%). melting range: 155-.1H NMR (400 MHz, CDCl3): δ 7.72 (d, J = 9.9 Hz, 1H), 7.65 (d, J = 1.2 Hz, 1H), 7.55 (d, J = 7.1 Hz, 2H), 7.50-7.35 (m, 7H), 7.33-7.23 (m, 2H), 7.13-6.98 (m, 6H), 6.91-6.87 (m, 2H), 6.45 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 196.8, 147.7, 146.2, 145.5, 145.0, 144.9, 141.0, 139.8, 135.3, 135.2, 134.4, 130.2, 129.6, 129.2, 129.0, 128.7, 128.1, 128.0, 127.9, 127.8, 127.5, 127.2, 127.1, 126.8, 126.5, 126.1, 122.0, 121.8, 120.9, 71.6. IR (KBr): 3058, 2924, 1663, 1561, 1490, 1453, 1268, 1223, 744, 697 cm-1. HRMS (ESI) m/z calculated for C34H22OSNa [M+Na]+ 501.1289, found 501.1289。
Example 31:
Figure DEST_PATH_IMAGE039
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3k, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 7' -Bromo-2, 3-diphenylene-2 ' H-spiro [ indene-1,1' -naphthalen]-2' -one (4j ʹ ʹ). And (3) product data characterization: yellow solid (80.8 mg, yield: 85%). melting range: 215-.1H NMR (400 MHz, CDCl3): δ 7.48 (d, J = 9.9 Hz, 1H), 7.46-7.41 (m, 2H), 7.37-7.24 (m, 4H), 7.22-7.12 (m, 3H), 6.99-6.87 (m, 6H), 6.78-6.71 (m, 2H), 6.30 (d, J = 9.9 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 195.7, 147.1, 145.4, 145.2, 145.1, 144.5, 143.2, 134.9, 134.1, 131.2, 131.0, 130.0, 129.6, 129.1, 129.0, 128.7, 128.2, 128.1, 127.3, 127.0, 126.6, 125.4, 122.2, 121.7, 71.4. IR (KBr): 3058, 2924, 1663, 1583, 1490, 1451, 1266, 841, 755, 698 cm-1. HRMS (ESI) m/z calculated for C30H19BrONa [M+Na]+ 497.0517, found 497.0517。
Example 32:
Figure DEST_PATH_IMAGE040
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of the reactant 1a, 0.3 mmol of the reactant 2b, 0.3 mmol of the reactant 3l, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 3' -Chloro-2, 3-diphenylene-2 ' H-spiro [ indole-1, 1' -naphthalen]-2' -one (4k ʹ ʹ). And (3) product data characterization: yellow solid (64.6 mg, yield: 75%). melting range: 131-.1H NMR (400 MHz, CDCl3): δ 7.89 (s, 1H), 7.54 (d, J = 7.1 Hz, 2H), 7.50-7.39 (m, 4H), 7.34-7.27 (m, 3H), 7.20 (t, J = 7.4 Hz, 1H), 7.11 (t, J = 7.1 Hz, 1H), 7.06-6.99 (m, 5H), 6.84 (d, J = 6.6 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ 189.6, 147.0, 145.4, 145.0, 144.5, 143.5, 140.1, 134.9, 134.0, 130.9, 130.8, 129.7, 129.6, 129.5, 129.1, 129.0, 128.3, 128.2, 128.1, 128.0, 127.3, 127.0, 126.7, 122.2, 121.8, 72.9. IR (KBr): 3059, 2923, 1677, 1603, 1492, 1451, 1267, 1229, 754, 697 cm-1. HRMS (ESI) m/z calculated for C30H19ClONa [M+Na]+ 453.1022, found 453.1023。
Example 33:
Figure DEST_PATH_IMAGE041
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of the reactant 1a, 0.3 mmol of the reactant 2b, 0.3 mmol of the reactant 3m, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 2,3-Diphenyl-6'H-spiro [ indole-1, 5' -quinolin]-6' -one (4l ʹ ʹ). And (3) product data characterization: white solid (31.0 mg, yield: 39%). melting range 104-105 ℃.1H NMR (400 MHz, CDCl3): δ 8.55 (d, J = 3.7 Hz, 1H), 7.87 (d, J = 10.1 Hz, 1H), 7.55-7.38 (m, 5H), 7.33-7.24 (m, 2H), 7.20 (dd, J = 7.9, 1.3 Hz, 1H), 7.13-6.97 (m, 6H), 6.82 (dd, J= 8.0, 1.5 Hz, 2H), 6.65 (d, J = 10.1 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 195.6, 149.3, 148.9, 147.2, 146.7, 145.6, 145.5, 144.2, 134.9, 134.6, 134.0, 130.7, 129.6, 129.1, 129.0, 128.4, 128.3, 128.2, 127.5, 126.7, 124.5, 122.3, 121.9, 71.1. IR (KBr): 3055, 2924, 1670, 1493, 1447, 1227, 1113, 795, 750, 698 cm-1. HRMS (ESI) m/z calculated for C29H19NONa [M+Na]+ 420.1364, found 420.1361。
Example 34:
Figure DEST_PATH_IMAGE042
to a 5.0 mL sealed tube were added 0.02 mmol of palladium acetate, 0.3 mmol of reactant 1a, 0.3 mmol of reactant 2b, 0.3 mmol of reactant 3n, 0.4 mmol of potassium phosphate, and 2.0 mL of 1, 4-dioxane in this order under argon, followed by heating to 130 ℃ in an oil bath and reacting for 16 hours. After the reaction is finished, directly spin-drying the reaction solution, and separating by column chromatography to obtain the target product 7' -Methoxy-2,3-diphenyl-2' H-spiro [ indole-1, 1' -naphthalene]-2' -one (4m ʹ ʹ). And (3) product data characterization: yellow solid (74.2 mg, yield: 87%). melting range: 209-210 ℃.1H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 9.9 Hz, 1H), 7.56-7.51 (m, 2H), 7.49-7.35 (m, 4H), 7.30-7.20 (m, 2H), 7.09-6.97 (m, 5H), 6.91-6.87 (m, 2H), 6.78 (dd, J = 8.4, 2.5 Hz, 1H), 6.51 (d, J = 2.5 Hz, 1H), 6.28 (d, J = 9.9 Hz, 1H), 3.63 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 196.6, 161.5, 147.9, 146.0, 145.3, 145.0, 144.7, 143.4, 135.3, 134.3, 131.5, 129.5, 129.2, 128.8, 128.0, 127.9, 127.7, 127.0, 126.3, 124.0, 123.0, 121.9, 121.5, 113.0, 112.6, 71.8, 55.2. IR (KBr): 3058, 2933, 2839, 1660, 1599, 1462, 1228, 1060, 1033, 872, 700, 645 cm-1 .HRMS (ESI) m/z calculated for C31H22O2Na [M+Na]+ 449.1517, found 449.1522。
Example 35: examples of the invention in the context of organic semiconductor light-emitting materials
Figure DEST_PATH_IMAGE043
The method comprises the following specific operation steps: 0.2 mmol of 4m ʹ ʹ was dissolved in 5.0 mL of dichloromethane solution, the temperature of the reaction solution was then lowered to 0 deg.C, boron tribromide was slowly added dropwise to the solution, which was then allowed to return to room temperature and stirred for 3 h. After the reaction is finished, quenching with water, extracting with dichloromethane, combining organic phases, then spin-drying to obtain a crude product 5, and separating and purifying by column chromatography to obtain a pure compound 5.
Data characterization of compound 5: yellow solid, yield: 92 percent.1H NMR (400 MHz, CD3COCD3): δ 7.56 (d, J = 9.9 Hz, 1H), 7.48-7.41 (m, 2H), 7.37 (t, J = 7.2 Hz, 2H), 7.34-7.26 (m, 2H), 7.23-7.18 (m, 2H), 7.17-7.12 (m, 1H), 7.01-6.87 (m, 5H), 6.85-6.77 (m, 2H), 6.70 (dd, J = 8.4, 2.5 Hz, 1H), 6.43 (d, J = 2.5 Hz, 1H), 6.20 (d, J= 9.9 Hz, 1H).
The spiro arene is an important organic semiconductor building unit, and the unique non-planar spiro conjugation effect, cross conformation and steric hindrance effect of the spiro arene can effectively improve the photoelectric property and device stability of the organic semiconductor material. The spirocyclohexenone compound prepared by the invention has the characteristics of both spirocyclic skeleton and electron deficiency of unsaturated ketene, and is a semiconductor receptor unit with abundant potential. In view of this, we remove the methyl group from the spiro product 4m ″ obtained by the invented technique under the action of boron tribromide, and convert it into a spiro compound 5 with more electron enrichment.
Figure DEST_PATH_IMAGE044
As shown in figure 1 and figure 2, the invention respectively makes spiro compound 5, 7-hydroxycoumarin 6, coumarin derivative 7 in 4.5 × 10-5 The concentration of mol/L is dissolved in NaHCO3NaOH (PH = 10, 10 mM, containing 1% ethanol) in buffer, and then the maximum absorption wavelength and fluorescence emission wavelength of the above three compounds were measured, respectively. The absorption wavelength of the spiro compound is 433 nm, and the fluorescence emission wavelength is 548 nm; the maximum absorption wavelength of the compound 7-hydroxycoumarin 6 is 365 nm, and the fluorescence emission wavelength is 457 nm; the absorption wavelength of the coumarin derivative 7 is 406 nm, and the fluorescence emission wavelength is 532 nm. Compared with 7-hydroxycoumarin, the spiro compound 5 is obviously red-shifted in both the maximum absorption wavelength and the fluorescence emission wavelength, and also red-shifted in comparison with the optimized all-carbon coumarin. In addition to this, the pK of Compound 5a= 7.99, pK of compound 6a= 7.56, pK of compound 7a= 8.35, spiro compound 5 has pK of the spiro skeleton closer to standard coumarin than all-carbon coumarin derivative 7aTherefore, the spiro framework is more stable, and fully embodies the application value of the novel spiro framework in the aspect of organic semiconductor luminescent materials.

Claims (3)

1. A synthesis method of a spiro compound is characterized in that: adding a double-halogen compound 1, alkyne 2 and a 2-naphthol compound 3 shown in the following formula into a reaction solvent 1, 4-dioxane, taking palladium acetate as a catalyst, potassium phosphate as alkali, wherein the amount of the potassium phosphate is 1-3 times of that of the double-halogen compound 1, reacting under the protection of inert gas, and separating and purifying to obtain a spiro compound 4;
Figure 82377DEST_PATH_IMAGE001
R1and R2Ph, R 'is H, X, X' and R are the following groups,
Figure 32010DEST_PATH_IMAGE002
；
alternatively, the first and second electrodes may be,
r is H, X is I, X 'is Br, R' is H, R1And R2Is a group represented by the following formula (I),
Figure 573325DEST_PATH_IMAGE003
；
alternatively, the first and second electrodes may be,
r is H, X is I, X 'is Br, R' is H,
alkyne 2 is
Figure 317421DEST_PATH_IMAGE004
Spiro compound 4 is of the formula:
Figure 947117DEST_PATH_IMAGE005
，
alkyne 2 is
Figure 562424DEST_PATH_IMAGE006
Spiro compound 4 is of the formula:
Figure 915171DEST_PATH_IMAGE007
，
alkyne 2 is
Figure 141753DEST_PATH_IMAGE008
Spiro compound 4 is of the formula:
Figure 131181DEST_PATH_IMAGE009
，
alkyne 2 is
Figure 281671DEST_PATH_IMAGE010
Spiro compound 4 is of the formula:
Figure 678804DEST_PATH_IMAGE011
；
alternatively, the first and second electrodes may be,
r is H, X is I, X' is Br, R1And R2Is Ph, R' is the following group: 6-Cl, 6-Br, 6-CO2Et, 6-Ac, 6-CN, 6-OMe, 6-OTBS, 6-Ph, 6- (2-thiophene), 7-Br, 3-Cl or 7-OMe.
2. The method for synthesizing a spiro compound according to claim 1, wherein: the molar ratio of the double halogen compound 1, the alkyne 2 and the 2-naphthol compound 3 is (1-2): 1-2).
3. The method for synthesizing a spiro compound according to claim 1, wherein: the reaction temperature is 100-150 ℃.
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