A method for synthesizing 1-oxodibenzo[a,kl]xanthene-13c(1h)-carbonitrile

Abstract

The present application relates to a kind of synthesis method of 1-oxysubstituted dibenzo [a, kl] oxepin-13 c (1H) -carbonitrile, which refers to substrate binaphthol and high-valence iodine reagent are dissolved in solvent, then trimethyl cyanosilane (TMSCN) is added, stirred at room temperature for 2~5 hours, then quenched by water, the obtained mixture is extracted with ethyl acetate for 3 times, then the organic phase is combined;The organic phase is dried, concentrated under reduced pressure, and then column chromatography with petroleum ether-ethyl acetate, to obtain light yellow solid 1-oxysubstituted dibenzo [a, kl] oxepin-13 c (1H) -carbonitrile.The present application has the characteristics of cheap and easy-to-obtain raw materials, mild reaction conditions, environmental friendliness, simple operation and excellent yield.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, and in particular to a method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. Background Technology

[0002] Oxanthracenes are a class of oxygen-containing heterocyclic compounds with a dibenzopyran skeleton. Due to their potential applications in fluorescent probes, laser dyes, pharmaceuticals, and food additives, these compounds play an important role in the pharmaceutical and industrial fields. For example, fluorescein is a commonly used probe for detecting H2O2 in living cells, Rhodamine 6G is a classic reference dye for evaluating the effects of other dyes, Blumeaxanthene is a traditional Chinese medicine for treating gynecological diseases, and phloxine is commonly used as a coloring agent in candies, cookies, ice cream, etc.

[0003] As an oxanthracene compound, 1-oxonyldibenzo[a,kl]oxanthracene-13c(1H)-formonitrile also possesses certain biological activities. According to literature reports, this compound exhibits significant antitumor activity against liver cancer cells, cervical cancer cells, human bone sarcoma cells, and lung cancer cells. The currently reported synthetic method involves the reaction of alkoxylated oxanthracene with trimethylcyanosylsilane (TMSCN) in the presence of phosphoric acid (H3PO4). The synthetic route is shown below:

[0004]

[0005] Although the synthetic method achieves a yield of 80%, which is quite good, it has at least the following drawbacks: First, the alkoxylated xanthracene from which the starting material is derived is not a commercially available reagent and must be obtained through synthesis; second, it requires H3PO4 as the reaction medium, leaving residual acid, which is environmentally unfriendly; and third, the substrate range is relatively narrow, with limited tolerance to functional groups. Therefore, it is particularly necessary to develop a method with inexpensive and readily available starting materials that is also environmentally friendly. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a method for synthesizing 1-oxonide dibenzo[a,kl]oxanthracene-13c(1H)-formonitrile that is readily available and environmentally friendly.

[0007] To address the aforementioned problems, the present invention provides a method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile, characterized in that: the method involves dissolving the substrate binaphthol and a high-valent iodine reagent in a solvent, then adding trimethylcyanosilane (TMSCN), stirring the reaction at room temperature for 2-5 hours, quenching the reaction with water, extracting the resulting mixture three times with ethyl acetate, and combining the organic phases; the organic phase is dried, concentrated under reduced pressure, and subjected to petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile; the mass-to-volume ratio of binaphthol to the solvent is 1:50-100; the molar ratio of binaphthol, high-valent iodine reagent, and trimethylcyanosilane is 1:1.5-3.5:1.5-3.5.

[0008] The reaction equation for this synthesis method is:

[0009]

[0010] The solvent refers to any one of chlorinated alkane solvents, alcohol solvents, ether solvents, and aromatic solvents.

[0011] The chloroalkane solvent refers to any one of 1,2-dichloroethane, dichloromethane, and chloroform.

[0012] The alcohol solvent refers to methanol or anhydrous ethanol with a mass fraction ≥ 99.5%.

[0013] The ether solvent refers to any one of diethyl ether, tetrahydrofuran, and 1,4-dioxane.

[0014] The aromatic solvents refer to any one of benzene, toluene, and m-xylene.

[0015] The high-valent iodine reagent refers to any one of the following: iodobenzoylbenzene (PhIO), iodobenzoyl acetate (PIDA), iodobenzoyl bis(trifluoroacetic acid) (PIFA), hydroxy(p-toluenesulfonyl)iodobenzoylbenzene (Koser's reagent), 1-hydroxyiodobenzoylbenzene (IBX), and Dess-Martin reagent.

[0016] In the petroleum ether-ethyl acetate column chromatography, the volume ratio of petroleum ether to ethyl acetate is 3~30:1.

[0017] Compared with the prior art, the present invention has the following advantages:

[0018] 1. This invention uses commercially available binaphthol as a raw material, a relatively mild high-valent iodine reagent as an oxidant, and TMSCN as a cyanide source to react in a solvent at room temperature, thereby obtaining 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile in excellent yield.

[0019] 2. The product obtained by this invention is a light yellow solid, which, after being processed... 1 H NMR, 13 C NMR and HRMS testing (see [reference]) Figure 1-3 ), mp198~199 ℃.

[0020] 1 H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.74 (d, J = 8.5 Hz, 1H), 7.57-7.54 (m, 1H), 7.50-7.46 (m, 1H), 7.44 (d, J =10.0 Hz, 1H), 7.42-7.39 (m, 1H), 7.30 (d, J = 9.0 Hz, 1H), 7.12 (t, J = 8.0 Hz, 2H), 6.40 (d, J = 10.5 Hz, 1H).

[0021] 13 C NMR (125 MHz, CDCl3) δ 190.4, 149.5, 148.8, 142.1, 132.8, 132.1, 131.3, 131.2, 131.1, 128.8, 126.8, 125.3, 125.2, 125.1, 124.5, 118.0, 117.9, 117.6, 113.2, 104.6, 45.0.

[0022] HRMS (ESI) calculates C 21 H 11 NO2Na [M+Na] + 332.06820, the result is 332.06822.

[0023] The test results show that it is consistent with the target molecule.

[0024] 3. X-ray single-crystal diffraction tests were performed on the product of this invention (see...). Figure 4 And Table 1, for ease of observation, single crystal diffraction. Figure 4 (The other target molecule and diethyl ether were omitted in the process), and the results showed that the product was the target molecule and the structure was correct.

[0025] Table 1 Crystal data and structure

[0026]

[0027] 4. The raw materials for this invention are inexpensive and readily available, the reaction conditions are mild and environmentally friendly, and the operation is simple. Attached Figure Description

[0028] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings.

[0029] Figure 1 For the present invention 1 H NMR spectrum.

[0030] Figure 2 For the present invention 13 C NMR spectrum.

[0031] Figure 3 This is the HRMS diagram of the present invention.

[0032] Figure 4 This is the X-ray single-crystal diffraction pattern of the present invention (the other target molecule and the diethyl ether molecule have been removed from the figure for easier observation). Detailed Implementation

[0033] A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile is disclosed. The method involves dissolving the substrate naphthol in a solvent with a high-valent iodine reagent, adding trimethylcyanosilane (TMSCN), stirring the reaction at room temperature for 2-5 hours, quenching the reaction with water, extracting the resulting mixture three times with ethyl acetate, and combining the organic phases. The organic phase is then dried, concentrated under reduced pressure, and subjected to petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid, 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile.

[0034] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:50~100; the molar ratio of binaphthol, high-valent iodine reagent, and trimethylcyanosilane is 1:1.5~3.5:1.5~3.5.

[0035] Solvents refer to any one of the following: chlorinated alkane solvents, alcohol solvents, ether solvents, and aromatic solvents.

[0036] Chlorinated alkane solvents refer to any one of 1,2-dichloroethane, dichloromethane, and chloroform.

[0037] Alcohol solvents refer to methanol or anhydrous ethanol with a mass fraction ≥ 99.5%.

[0038] Ether solvents refer to any one of diethyl ether, tetrahydrofuran, and 1,4-dioxane.

[0039] Aromatic solvents refer to any one of benzene, toluene, and m-xylene.

[0040] High-valent iodine reagents refer to any one of the following: iodobenzoylbenzene (PhIO), iodobenzoyl acetate (PIDA), iodobenzoyl bis(trifluoroacetic acid) (PIFA), hydroxy(p-toluenesulfonyloxy)iodobenzoylbenzene (Koser's reagent), 1-hydroxyiodobenzoylbenzene (IBX), and Dess-Martin reagent.

[0041] In petroleum ether-ethyl acetate column chromatography, the volume ratio (mL / mL) of petroleum ether to ethyl acetate is 3~30:1.

[0042] Example 1: A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until the binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid, 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile, with a yield of 58%.

[0043] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PhIO.

[0044] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0045] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2:2.

[0046] In petroleum ether-ethyl acetate column chromatography, the volume ratio (mL / mL) of petroleum ether to ethyl acetate is 6:1.

[0047] Reduced pressure concentration conditions refer to distillation under reduced pressure using a rotary evaporator at a pressure of 0.075 MPa.

[0048] Example 2. A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 47%.

[0049] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PhIO.

[0050] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0051] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:1.5:2.

[0052] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0053] Example 3. A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 75%.

[0054] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PhIO.

[0055] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0056] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.

[0057] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0058] Example 4. A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 70%.

[0059] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PhIO.

[0060] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0061] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:1.5.

[0062] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0063] Example 5. A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 51%.

[0064] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PhIO.

[0065] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0066] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:1.

[0067] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0068] Example 6. A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol is completely reacted, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 88%.

[0069] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PhIO.

[0070] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0071] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0072] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0073] Example 7 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 81%.

[0074] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PhIO.

[0075] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0076] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:3.

[0077] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0078] Example 8. A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 72%.

[0079] Wherein: the solvent refers to dichloromethane. The high-valent iodine reagent refers to PhIO.

[0080] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0081] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0082] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0083] Example 9. A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 64%.

[0084] Wherein: solvent refers to chloroform. High-valent iodine reagent refers to PhIO.

[0085] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0086] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0087] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0088] Example 10 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol is completely reacted, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 54%.

[0089] Wherein: the solvent refers to methanol with a mass fraction ≥ 99.5%. High-valent iodine reagent refers to PhIO.

[0090] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0091] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0092] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0093] Example 11 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 65%.

[0094] Wherein: the solvent refers to anhydrous ethanol. The high-valent iodine reagent refers to PhIO.

[0095] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0096] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0097] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0098] Example 12 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 85%.

[0099] Wherein: the solvent refers to acetonitrile. The high-valent iodine reagent refers to PhIO.

[0100] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0101] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0102] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0103] Example 13 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 80%.

[0104] Wherein: the solvent refers to tetrahydrofuran. The high-valent iodine reagent refers to PhIO.

[0105] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0106] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0107] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0108] Example 14 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 58%.

[0109] Wherein: the solvent refers to benzene. The high-valent iodine reagent refers to PhIO.

[0110] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0111] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0112] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0113] Example 15 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 61%.

[0114] Wherein: the solvent refers to toluene. The high-valent iodine reagent refers to PhIO.

[0115] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0116] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0117] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0118] Example 16 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 66%.

[0119] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PIDA.

[0120] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0121] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0122] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0123] Example 17 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol is completely reacted, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 56%.

[0124] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to PIFA.

[0125] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0126] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0127] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0128] Example 18 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 61%.

[0129] The solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to Koser's reagent.

[0130] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0131] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0132] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

[0133] Example 19 A method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile. The method involves weighing binaphthol and high-valent iodine reagent into a round-bottom flask, adding solvent and TMSCN, stirring at room temperature until binaphthol reacts completely, quenching with water, extracting the mixture three times with ethyl acetate, combining the organic phases, drying and concentrating them, and then precipitating the residue by petroleum ether-ethyl acetate column chromatography to obtain a light yellow solid 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile with a yield of 58%.

[0134] Wherein: the solvent refers to 1,2-dichloroethane. The high-valent iodine reagent refers to Dess-Martin's reagent.

[0135] The mass-to-volume ratio (g / mL) of binaphthol to solvent is 1:60.

[0136] The molar ratio of binaphthol, high-valent iodine reagent, and TMSCN is 1:2.5:2.5.

[0137] The column chromatography and vacuum concentration conditions for petroleum ether-ethyl acetate were the same as in Example 1.

Claims

1. A method of synthesis of 1-oxo- benz[a,kl]xanthene-13c(lH)-carbonitrile, characterized by: The method comprises the following steps: dissolving substrates binaphthol and high-valence iodine reagent in a solvent, then adding trimethylsilyl cyanide, stirring at room temperature for 2-5 hours, adding water to quench the reaction, extracting the obtained mixture with ethyl acetate for 3 times, combining the organic phase, drying the organic phase, reducing pressure and concentrating, and then performing petroleum ether-ethyl acetate column chromatography to obtain light yellow solid 1-oxodibenzo[a,kl]oxepin-13c(1H)-carbonitrile; the mass-volume ratio of the binaphthol to the solvent is 1 g: 50-100 mL; the molar ratio of the binaphthol, the high-valence iodine reagent and the trimethylsilyl cyanide is 1: 1.5-3.5: 1.5-3.5; the high-valence iodine reagent refers to any one of iodosylbenzene, iodobenzene acetate, iodobenzene bistrifluoroacetate, hydroxyl (p-toluenesulfonyloxy) iodobenzene and Dess-Martin reagent.

2. A process for the synthesis of 1-oxylbenzo[a,kl]xanthene-13c(lH)-carbonitrile according to claim 1, characterized by: The solvent refers to any one of chlorinated alkane solvents, alcohol solvents, ether solvents and aromatic hydrocarbon solvents.

3. A process for the synthesis of 1-oxylbenzo[a,kl]xanthene-13c(lH)-carbonitrile according to claim 2, characterized by: The chlorinated alkane solvent refers to any one of 1,2-dichloroethane, dichloromethane and chloroform.

4. A process for the synthesis of 1-oxylbenzo[a,kl]xanthene-13c(lH)-carbonitrile as claimed in claim 2, wherein: The alcohol solvent refers to methanol or anhydrous ethanol with a mass fraction of ≥99.5%.

5. A process for the synthesis of 1-oxylbenzo[a,kl]xanthene-13c(lH)-carbonitrile as claimed in claim 2, wherein: The ether solvent refers to any one of diethyl ether, tetrahydrofuran and 1,4-dioxane.

6. A process for the synthesis of 1-oxylbenzo[a,kl]xanthene-13c(lH)-carbonitrile as claimed in claim 2, wherein: The aromatic hydrocarbon solvent refers to any one of benzene, toluene and m-xylene.

7. The method for synthesizing 1-oxomethylenedibenzo[a,kl]oxanthracene-13c(1H)-formonitrile as described in claim 1, characterized in that: The volume ratio of petroleum ether to ethyl acetate in the petroleum ether-ethyl acetate column chromatography is 3-30:1.

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