METHOD FOR PREPARING CYCLIC PHOSPHATE COMPOUND AND DERIVATIVE THEREOF

Abstract

Provided is a method for preparing a cyclic phosphate compound represented by formula (III) or formula (IV) and a derivative thereof. The method includes: step 1), adding a compound of formula (I), a compound of formula (II), and a solvent to a reactor, and then adding white phosphorus and a first base in sequence, followed by heating while stirring to obtain a mixed solution of reactants; and step 2), adding a second base to the mixed solution of reactants, and subjecting a resulting mixture to heating and reaction; at end of the reaction, stopping the heating and then cooling a resulting reaction product to room temperature; and adding an acid to the reactor and conducting acidification to obtain a compound of formula (III) or a compound of formula (IV).

##STR00001##

Claims

1. A method for preparing a cyclic phosphate compound and a derivative thereof, the cyclic phosphate compound being a compound of formula (III) or a compound of formula (IV) each containing a diaryl structural unit, ##STR00022## wherein in the formula (III) or the formula (IV), R.sup.1 represents one selected from the group consisting of hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, thienyl, and a benzo group; Ar represents one selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, and thienyl; and n represents carbon number and is an integer of 0 or greater than 0; and the method comprising: ##STR00023## step 1) adding a compound of formula (I), a compound of formula (II), and a solvent to a reactor, and then adding white phosphorus and a first base in sequence, followed by heating while stirring to obtain a mixed solution of reactants; and step 2) adding a second base to the mixed solution of reactants obtained in step 1), and subjecting a resulting mixture to heating and reaction; at end of the reaction, stopping the heating and then cooling a resulting reaction product to room temperature; and adding an acid to the reactor and conducting acidification to obtain the compound of formula (III) or the compound of formula (IV), wherein in the formula (I) and the formula (II), R.sup.1 and R.sup.2 independently represent one selected from the group consisting of hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, and thienyl; Ar in the formula (I) represents one selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, and thienyl; n in the formula (I) represents carbon number and is an integer of 0 or greater than 0; and X in the formula (II) represents one selected from the group consisting of S, Se, and Te.

2. The method of claim 1, wherein in step 1), the first base is selected from the group consisting of a hydroxide, a carbonate, a phosphate or an organic alkoxide of an alkali metal, and an organic amine.

3. The method of claim 1, wherein in step 1), the heating is conducted at a temperature of 40 C. to 120 C. for 2 hours to hours.

4. The method of claim 1, wherein in step 1), a molar amount of the compound of formula (I) is 1.0 time to 1.5 times a molar equivalent of phosphorus atoms in the white phosphorus, a molar amount of the compound of formula (II) is 0.2 times to 2.0 times the molar equivalent of the phosphorus atoms in the white phosphorus, and a molar amount of the first base is 0.2 times to 2.0 times the molar equivalent of the phosphorus atoms in the white phosphorus.

5. The method of claim 1, wherein in step 2), under a condition for synthesis of the compound of formula (III), the second base is selected from the group consisting of a hydroxide, a carbonate, a phosphate or an organic alkoxide of an alkali metal, and an organic amine; and under a condition for synthesis of the compound of formula (IV), the second base is selected from the group consisting of sodium hydrosulfide, potassium hydrosulfide, sodium sulfide, and ammonium sulfide.

6. The method of claim 1, wherein in step 2), the acid used for the acidification is a strong inorganic acid, and the acidification is conducted until a resulting acidification system has a pH of 1 to 3.

7. The method of claim 1, wherein in step 2), after adding the second base, the reaction is conducted at a temperature of 120 C. for 1 hour to 8 hours.

8. The method of claim 1, wherein in step 2), a molar amount of the second base is 1.0 time to 2.5 times a molar equivalent of phosphorus atoms in the white phosphorus.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

[0029] The foregoing summary of the present disclosure is described in further detail below by way of specific embodiments, which, however, should not be construed as limiting in any way the scope of the present disclosure. All technical solutions realized based on the content of the present disclosure described above are within the scope of the present disclosure. The present disclosure provides a general and/or specific description of the materials used in the tests and the test methods. It is clear to a person skilled in the art that in the following, if not specifically stated, the room temperature described in the present disclosure has technical meanings known in the art, typically 20 C. to 25 C.; and all of the chemicals described are commercially available.

[0030] The present disclosure provides a method for preparing a cyclic phosphate compound and a derivative thereof, the cyclic phosphate compound being a compound of formula (III) or a compound of formula (IV) each containing a diaryl structural unit.

##STR00004##

[0031] In the present disclosure, in the formula (III) or the formula (IV): R.sup.1 represents hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, an alkyl group of any carbon number, an alkoxy group of any carbon number, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, thienyl, a benzo group, etc.; Ar represents an aromatic ring group such as phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, and thienyl; and n represents carbon number and is an integer of 0 or greater than 0. In some embodiments, n is 0 or 1.

[0032] In some embodiments, the substituted or unsubstituted phenyl and the substituted or unsubstituted biphenyl each have the same meanings as the definition given above.

Preparation of Compounds

[0033] A method for preparing a cyclic phosphate compound includes the following steps:

##STR00005## [0034] step 1), a compound of formula (I), a compound of formula (II), and a solvent are added to a reactor, and after dissolving same, white phosphorus and a first base are added in sequence, followed by heating while stirring to obtain a mixed solution of reactants; and [0035] step 2): a second base is added to the mixed solution of reactants obtained in step 1), and a resulting mixture is subjected to heating and reaction; at end of the reaction, the heating is stopped and then a resulting reaction product is cooled to room temperature; and an acid is added to the reactor and acidification is conducted to obtain a compound of formula (III).

[0036] A method for preparing a derivative of a cyclic phosphate compound includes the following steps:

##STR00006## [0037] step 1): a compound of formula (I), a compound of formula (II), and a solvent are added to a reactor, and after dissolving same, white phosphorus and a first base are added in sequence, followed by heating and stirring to obtain a mixed solution of reactants; and [0038] step 2): a second base is added to the mixed solution of reactants obtained in step 1), and a resulting mixture is subjected to heating and reaction; at end of the reaction, the heating is stopped and then a resulting reaction product is cooled to room temperature; and an acid is added to the reactor and acidification is conducted to obtain a compound of formula (IV).

[0039] In the present disclosure, in both the reaction equations described above, for the compound of formula (I), R.sup.1 represents hydrogen, halogen, alkenyl, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, thienyl, etc.; Ar represents an aromatic ring group, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, and thienyl; and n represents carbon number and is an integer of 0 or greater than 0.

[0040] In the present disclosure, in the formula (II), X represents S, Se, or Te; and R.sup.2 represents hydrogen, halogen, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, thienyl, etc.

[0041] In the present disclosure, in the formula (III) or the formula (IV), R.sup.1 represents hydrogen, halogen, nitro, cyano, trifluoromethyl, trifluoromethoxy, alkyl, alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, thienyl, a benzo group etc.; Ar represents an aromatic ring group, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, and thienyl; and n represents carbon number and is an integer of 0 or greater than 0.

[0042] In some embodiments, the substituted or unsubstituted phenyl and the substituted or unsubstituted biphenyl each have the same meanings as the definition given above for R.sup.1 and R.sup.2.

[0043] In some embodiments, in step 1) of both the reaction equations described above, the first base is selected from the group consisting of a hydroxide, a carbonate, a phosphate or an organic alkoxide of an alkali metal, and an organic amine, preferably the organic amine.

[0044] In some embodiments, the solvent used in both the reaction equations described above needs to contain dialkyl sulfoxide, which is a solvent of dialkyl sulfoxide alone or a mixture thereof with other solvents in a volume ratio of 100:1 to 0:1. The other solvent may be any organic solvent as long as it does not react with the compound of formula (I), the compound of formula (II), white phosphorus, and dialky sulfoxide, for example, acetonitrile (MeCN), tetrahydrofuran (THF), diethyl ether (Et.sub.2O), acetone, benzene, toluene, 1,4-dioxane, dimethoxyethane (DME), or tetramethylethylenediamine (TMEDA). Preferably, the solvent is dimethyl sulfoxide (DMSO) alone.

[0045] In some embodiments, in step 1) of both the reaction equations described above, the heating is conducted at a temperature of 40 C. to 120 C. for 2-8 hours.

[0046] In some embodiments, in step 1) of both the reaction equations described above, a molar amount of the compound of formula (I) and the compound of formula (II) is in a range of 1.0-1.5 times and 0.2-2.0 times a molar equivalent of the white phosphorus (P.sub.4), respectively, and a molar amount of the first base is 0.2-2.0 times the molar equivalents of the white phosphorus (P.sub.4).

[0047] In some embodiments, in step 2), the second base for synthesis of the compound of formula (III) is selected from the group consisting of a hydroxide, a carbonate, a phosphate or an organic alkoxide of an alkali metal, and an organic amine, where the alkali metal is potassium or sodium; and potassium hydroxide is preferred. The second base for synthesis of the compound of formula (IV) is selected from the group consisting of sodium hydrosulfide, potassium hydrosulfide, sodium sulfide, and ammonium sulfide, preferably sodium hydrosulfide.

[0048] In some embodiments, the acid used for the acidification in step 2) of both the reaction equations described above is a strong inorganic acid, such as sulfuric acid (H.sub.2SO.sub.4), nitric acid (HNO.sub.3), hydrochloric acid (HCl), perchloric acid (HClO.sub.4), permanganic acid (HMnO.sub.4), hydroiodic acid (HI), and hydrobromic acid (HBr), preferably hydrochloric acid (HCl) or hydrobromic acid (HBr).

[0049] In some embodiments, in step 2) of both the reaction equations described above, after adding the second base, the reaction is conducted at a temperature of room temperature to 120 C., preferably 60-80 C., and the reaction is conducted for 1-8 hours, preferably 2-5 hours.

[0050] In some embodiments, in step 2) of both the reaction equations described above, in the acidification step, the acidification is conducted at room temperature, and the acidification is conducted for 0.5-4 hours, preferably 1-3 hours.

[0051] In some embodiments, in step 2) of both the reaction equations described above, a molar amount of the second base is in a range of 1.0-2.5 times, preferably 1.5-2.0 times, a molar equivalents of the white phosphorus (P.sub.4) in step 1).

[0052] In some embodiments, in step 2) of both the reaction equations described above, an amount of the acid is controlled according to pH, and the acidification is conducted until a resulting acidification system has a pH of 1-3.

[0053] In some embodiments, the solvents used in the steps 1) of both the reaction equations described above may be the same or different. For ease of operation and workup, it is preferable to carry out the operation of step 2) directly in the reaction solution of step 1) without the need for purification and separation of the reaction product of step 1).

[0054] As can be seen from the methods described above, the method disclosed in the present disclosure shows mild reaction conditions, relatively short reaction time, and simple workup operations (as can be known from the reaction operations in the examples below), while resulting in high yields.

[0055] The method for preparing the compounds described above is described in detail in the following examples.

Synthesis of a Compound of Formula (III) or Formula (IV)

Example 1: Synthesis of (S)-3,3-dimethyl-1,1-binaphthol Hydrogen Phosphate

##STR00007##

[0056] In a glove box filled with nitrogen, (S)-3,3-dimethyl-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atoms, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were added thereto in sequence. A resulting reaction mixture was stirred at 80 C. for 4 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 3 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 3, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 90% yield (yield calculated on phosphorus atoms).

[0057] Main nuclear magnetic resonance (NMR) data: .sup.1H NMR (500 MHZ, CD3OD): 2.67 (s, 6H), 7.13-7.18 (m, 4H), 7.35-7.39 (m, 2H), 7.83-7.85 (m, 4H); .sup.13C NMR (150 MHZ, CD3OD): 18.0, 123.4, 125.9, 126.2, 127.7, 128.7, 130.8, 132.0, 132.7, 149.7 (d, J=9.5 Hz); 31P NMR (243 MHz, CD3OD): 2.4; HRMS calcd for [C22H1704P] ([M+H].sup.+): 377.0938, found 377.0937.

Example 2: Synthesis of (Rac)-binaphthol Hydrogen Phosphate

##STR00008##

[0058] In a glove box filled with nitrogen, (Rac)-binaphthol (0.36 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 3 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 2 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 2, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 91% yield (yield calculated on phosphorus atoms).

[0059] Main NMR data: .sup.1H NMR (600 MHZ, CD.sub.3OD): 7.30-7.34 (m, 4H), 7.50-7.53 (m, 2H), 7.58 (d, J=8.9 Hz, 2H), 8.03 (d, J=8.4 Hz, 2H), 8.13 (d, J=8.9 Hz, 2H); .sup.13C NMR (150 MHz, CD.sub.3OD): 121.8, 122.8, 126.7, 127.8, 129.7, 132.3, 133.1, 133.6, 148.8 (d, J=9.7 Hz); .sup.31P NMR (243 MHZ, CD.sub.3OD): 3.7; HRMS calcd for [C.sub.20H.sub.13O.sub.4P] ([M+H].sup.+): 349.0625, found 349.0628.

Example 3: Synthesis of (R)-3,3-dimethoxy-1,1-binaphthol Phosphate

##STR00009##

[0060] In a glove box filled with nitrogen, (R)-3,3-dimethoxy-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), diphenyl diselenide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 60 C. for 5 hours, then KOH (0.6 mmol) was added and alkaline hydrolysis was continued at 70 C. for 4 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 3, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 82% yield (yield calculated on phosphorus atoms).

[0061] Main NMR data: .sup.1H NMR (500 MHZ, CD.sub.3OD): 4.03 (s, 6H), 7.03-7.13 (m, 4H), 7.35 (t, J=7.5 Hz, 2H), 7.53 (s, 2H), 7.84 (d, J=8.3 Hz, 2H); .sup.13C NMR (125 MHz, CD.sub.3OD): 56.6, 109.9, 124.2 (d, J=2.7 Hz), 125.3, 127.2, 127.7, 128.0, 128.5, 133.6, 140.3 (d, J=9.2 Hz), 151.6 (d, J=2.7 Hz); .sup.31P NMR (202 MHZ, CD.sub.3OD): 3.5; HRMS calcd for [C.sub.22H.sub.17O.sub.6P] ([M+H].sup.+): 409.0836, found 409.0836.

Example 4: Synthesis of (R)-3,3-diphenyl-1,1-binaphthol Hydrogen Phosphate

##STR00010##

[0062] In a glove box filled with nitrogen, (R)-3,3-diphenyl-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 5 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 3 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 1, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 89% yield (yield calculated on phosphorus atoms).

[0063] Main NMR data: .sup.1H NMR (600 MHZ, CD.sub.3OD): 7.19-7.25 (m, 4H), 7.31-7.33 (m, 2H), 7.40 (t, J=7.7 Hz, 4H), 7.45 (t, J=7.5 Hz, 2H), 7.77 (d, J=7.6 Hz, 4H), 8.00 (d, J=8.2 Hz, 2H), 8.05 (s, 2H); .sup.13C NMR (150 MHz, CD.sub.3OD): 124.1, 126.7, 127.5, 127.7, 128.5, 129.2, 129.6, 131.2, 132.2, 132.7, 133.4, 135.6, 139.0, 146.9 (d, J=9.0 Hz); .sup.31P NMR (243 MHz, CD.sub.3OD): 1.7; HRMS calcd for [C.sub.32H.sub.21O.sub.4P] ([M+H].sup.+): 501.1251, found 501.1253.

Example 5: Synthesis of (S)-3,3-dibromo-1,1-binaphthol Hydrogen Phosphate

##STR00011##

[0064] In a glove box filled with nitrogen, (R)-3,3-dibromo-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), 4,4-dichlorodiphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 6 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 2 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 2, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 88% yield (yield calculated on phosphorus atoms).

[0065] Main NMR data: .sup.1H NMR (500 MHZ, CD.sub.3OD): 6.98 (d, J=8.6 Hz, 2H), 7.11 (t, J=7.3 Hz, 2H), 7.34 (t, J=7.6 Hz, 2H), 7.80 (d, J=8.3 Hz, 2H), 8.30 (s, 2H); .sup.13C NMR (125 MHz, CD.sub.3OD): 115.6 (d, J=2.3 Hz), 124.2, 127.5, 127.6, 128.2, 128.8, 132.4, 133.2, 135.0, 145.4 (d, J=9.1 Hz); .sup.31P NMR (202 MHZ, CD.sub.3OD): 2.2; HRMS calcd for [C.sub.20H.sub.11Br.sub.2O.sub.4P] ([M+H].sup.+): 506.8814, found 506.8822.

Example 6: Synthesis of (R)-3,3-bis(4-methoxyphenyl)-1,1-binaphthol Hydrogen Phosphate

##STR00012##

[0066] In a glove box filled with nitrogen, (R)-3,3-bis(4-methoxyphenyl)-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), 4,4-difluorodiphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 5 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 4 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 3, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 90% yield (yield calculated on phosphorus atoms).

[0067] Main NMR data: .sup.1H NMR (600 MHz, CDCl.sub.3): 3.50 (s, 6H), 6.80 (d, J=7.1 Hz, 4H), 7.22-7.33 (m, 4H), 7.44-7.51 (m, 6H), 7.92 (t, J=8.3 Hz, 4H); .sup.13C NMR (150 MHz, CDCl.sub.3): 55.1, 113.9, 122.6, 126.0, 126.4, 127.2, 128.4, 129.2, 131.0, 131.2, 131.7, 131.9, 133.8, 144.8 (d, J=8.3 Hz), 159.3; 31P NMR (243 MHZ, CDCl.sub.3): 2.6; HRMS calcd for [C.sub.34H.sub.25O.sub.6P] ([M+H].sup.+): 561.1462, found 561.1463.

Example 7: Synthesis of (R)-3,3-bis(4-nitrophenyl)-1,1-binaphthol Hydrogen Phosphate

##STR00013##

[0068] In a glove box filled with nitrogen, (R)-3,3-bis(4-nitrophenyl)-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 6 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 2 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 2, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 84% yield (yield calculated on phosphorus atoms).

[0069] Main NMR data: .sup.1H NMR (600 MHz, CDCl.sub.3/CD.sub.3OD=14:1): 7.37 (br, 2H), 7.55 (br, .sup.1H), 7.81 (br, 2H), 8.00-8.03 (m, 2H), 8.16 (br, 2H); .sup.13C NMR (150 MHz, CDCl.sub.3/CD.sub.3OD =14:1): 122.9, 123.3, 126.4, 127.0, 127.4, 128.6, 130.8, 131.2, 131.6, 131.8, 132.5, 143.8, 144.3 (d, J=7.2 Hz), 147.1; 31P NMR (243 MHz, CDCl.sub.3/CD.sub.3OD=14:1): 1.6; HRMS calcd for [C.sub.32H.sub.19N.sub.2O.sub.8P] ([MH].sup.+): 589.0806, found 589.0805.

Example 8: Synthesis of (R)-3,3-bis(2,4,6-trimethylphenyl)-1,1-binaphthol Hydrogen Phosphate

##STR00014##

[0070] In a glove box filled with nitrogen, (R)-3,3-bis(2,4,6-trimethylphenyl)-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), 4,4-dichlorodiphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 6 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 60 C. for 4 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 1, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 90% yield (yield calculated on phosphorus atoms).

[0071] Main NMR data: .sup.1H NMR (500 MHZ, CDCl.sub.3): 1.90 (s, 6H), 2.00 (s, 6H), 2.06 (s, 6H), 6.60 (s, 2H), 6.75 (s, 2H), 7.22-7.33 (m, 4H), 7.42 (t, J=7.4 Hz, 2H), 7.65 (s, 2H), 7.87 (d, J=8.0 Hz, 2H); .sup.13C NMR (125 MHz, CDCl.sub.3): 20.4, 21.0, 21.3, 122.8, 125.2, 126.1, 127.2, 127.5, 128.1, 128.2, 131.1, 131.2, 132.5, 133.1, 134.8, 137.1, 137.6, 137.9, 146.9 (d, J=10.0 Hz); .sup.31P NMR (202 MHZ, CDCl.sub.3): 4.3; HRMS calcd for [C.sub.38H.sub.33O.sub.4P] ([MH].sup.+): 583.2043, found 583.2035.

Example 9: Synthesis of (S)-6,6-dibromo-1,1-binaphthol Hydrogen Phosphate

##STR00015##

[0072] In a glove box filled with nitrogen, (S)-6,6-dibromo-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), 4,4-dibromodiphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 6 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 2 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 3, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 83% yield (yield calculated on phosphorus atoms).

[0073] Main NMR data: .sup.1H NMR (500 MHZ, DMSO-d6): 7.14 (d, J=9.0 Hz, 2H), 7.50 (dd, J=9.3 Hz, J=2.0 Hz, 2H), 7.55 (d, J=9.0 Hz, 2H), 8.12 (d, J=8.8 Hz, 2H), 8.36 (d, J=1.8 Hz, 2H); .sup.13C NMR (125 MHz, DMSO-d6): 118.2, 121.2, 123.2, 128.1, 129.6, 129.9, 130.3, 132.0, 149.2 (d, J=9.5 Hz); .sup.31P NMR (202 MHZ, DMSO-d6): 3.0; HRMS calcd for [C.sub.20H.sub.11Br.sub.2O.sub.4P] ([MH].sup.+): 504.8668, found 504.8670.

Example 10: Synthesis of (R)-VANOL Hydrogen Phosphate

##STR00016##

[0074] In a glove box filled with nitrogen, (2R)-3,3-diphenyl [2,2-binaphthylyl]-1,1-diol (0.33 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 5 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 3 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 1.5, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 83% yield (yield calculated on phosphorus atoms).

[0075] Main NMR data: .sup.1H NMR (600 MHz, CD.sub.3OD): 6.48 (d, J=7.6 Hz, 4H), 6.92 (t, J=7.5 Hz, 4H), 7.10 (t, J=7.3 Hz, 2H), 7.51 (s, 2H), 7.59 (t, J=7.3 Hz, 2H), 7.65 (t, J=7.9 Hz, 2H), 7.88 (d, J=8.1 Hz, 2H), 8.47 (d, J=8.1 Hz, 2H); .sup.13C NMR (150 MHz, CD.sub.3OD): 123.7, 124.3 (d, J=2.1 Hz), 127.2 (d, J=2.2 Hz), 127.3, 127.7, 127.9, 128.6, 128.8, 128.9, 130.1, 135.7, 141.4, 141.5, 147.7 (d, J=9.8 Hz); .sup.31P NMR (243 MHZ, CD.sub.3OD): 3.2; HRMS calcd for [C.sub.32H.sub.21O.sub.4P] ([MH].sup.+): 499.1104, found 499.1106.

Example 11: Synthesis of 2,2-biphenol Hydrogen Phosphate

##STR00017##

[0076] In a glove box filled with nitrogen, 2,2-biphenol (0.36 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 uL toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 60 C. for 6 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 3 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 2, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 89% yield (yield calculated on phosphorus atoms).

[0077] Main NMR data: .sup.1H NMR (600 MHZ, CD.sub.3OD): 7.29 (d, J=8.0 Hz, 2H), 7.39 (t, J=7.5 Hz, 2H), 7.48 (d, J=7.5 Hz, 2H), 7.60-7.61 (m, 2H); .sup.13C NMR (150 MHz, CD.sub.3OD): 122.5 (d, J=4.4 Hz), 127.3, 130.1, 130.9, 131.1, 149.8 (d, J=9.1 Hz); .sup.31P NMR (243 MHZ, CD.sub.3OD): 2.5; HRMS calcd for [C.sub.12H.sub.9O.sub.4P] ([MH]): 247.0165, found 247.0165.

Example 12: Synthesis of 5,5-diallyl-2,2-biphenol Hydrogen Phosphate

##STR00018##

[0078] In a glove box filled with nitrogen, 5,5-diallyl-2,2-biphenol (0.36 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 4 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 3 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 1, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 83% yield (yield calculated on phosphorus atoms).

[0079] Main NMR data: .sup.1H NMR (600 MHZ, CD.sub.3OD): 3.47 (d, J=4.9 Hz, 4H), 5.08-5.14 (m, 4H), 5.98-6.04 (m, 2H), 7.20-7.39 (m, 6H); .sup.13C NMR (150 MHz, CD.sub.3OD): 40.4, 116.5, 122.3 (d, J=3.3 Hz), 129.8, 130.8, 131.2, 138.5, 139.8, 147.9 (d, J=9.7 Hz); .sup.31P NMR (243 MHZ, CD.sub.3OD): 2.6; HRMS calcd for [C.sub.18H.sub.1704P] ([MH]): 327.0791, found 327.0791.

Example 13: Synthesis of 3,3,5,5-tetramethyl-2,2-biphenol Hydrogen Phosphate

##STR00019##

[0080] In a glove box filled with nitrogen, 3,3,5,5-tetramethyl-2,2-biphenol (0.33 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 ml Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 4 hours, then KOH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 3 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 3, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 88% yield (yield calculated on phosphorus atoms).

[0081] Main NMR data: .sup.1H NMR (600 MHZ, CD.sub.3OD): 2.36 (s, 6H), 2.37 (s, 6H), 7.14 (s, 2H), 7.16 (s, 2H); .sup.13C NMR (150 MHz, CD.sub.3OD): 16.5, 20.9, 128.9, 130.0, 131.2 (d, J=3.8 Hz), 132.7, 136.7, 145.9 (d, J=9.5 Hz); .sup.31P NMR (243 MHz, CD.sub.3OD): 3.0; HRMS calcd for [C.sub.16H.sub.17O.sub.4P] ([MH].sup.+): 303.0791, found 303.0793.

Example 14: Synthesis of (S)-3,3-dimethyl-1,1-binaphthol Hydrogen Thiophosphate

##STR00020##

[0082] In a glove box filled with nitrogen, (S)-3,3-dimethyl-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 4 hours, then NaSH (0.6 mmol) was added thereto and reaction was continued at 80 C. for 3 hours. At the end of the reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 3, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 90% yield (yield calculated on phosphorus atoms).

[0083] Main NMR data: .sup.1H NMR (500 MHz, CDCl.sub.3): 2.42 (s, 3H), 2.54 (s, 3H), 7.06-7.16 (m, 4H), 7.28-7.36 (m, 2H), 7.46 (s, .sup.1H), 7.62 (d, J=8.2 Hz, .sup.1H), 7.72 (s, .sup.1H), 7.77 (d, J=8.4 Hz, .sup.1H); .sup.13C NMR (125 MHZ, CDCl.sub.3): 17.8, 18.4, 122.3, 122.7, 125.37, 125.43, 125.51, 125.68, 126.8, 127.0, 127.7, 129.8, 130.3, 130.57, 130.60, 131.11, 131.16, 131.4, 131.6, 147.3 (d, J=9.7 Hz), 147.8 (d, J=12.7 Hz); .sup.31P NMR (202 MHZ, CDCl.sub.3): 65.0.

Example 15: Synthesis of (R)-3,3-diphenyl-1,1-binaphthol Hydrogen Phosphate

##STR00021##

[0084] In a glove box filled with nitrogen, (R)-3,3-diphenyl-[1,1-binaphthylyl]-2,2-diphenol (0.33 mmol), diphenyl disulfide (80 mol %, 0.24 mmol), and DMSO (3 mL) were sequentially placed in a 10 mL Schlenk tube with a stirrer. Then a white phosphorus-toluene solution (9.3 mg P.sub.4, 0.3 mmol P-atom, dissolved in 320 L toluene) and Et.sub.3N (0.06 mmol) were sequentially added thereto. A resulting reaction mixture was stirred at 80 C. for 5 hours, then NaSH (0.6 mmol) was added thereto and alkaline hydrolysis was continued at 80 C. for 3 hours. At the end of reaction, dichloromethane and a 4 M dilute hydrochloric acid solution were added and subjected to acidification until a resulting acidification system had a pH of 1, and a resulting organic phase was extracted several times. A resulting combined organic phases were evaporated to dryness on a rotary evaporator and then a resulting crude reaction mixture was purified by flash chromatography to obtain a product in 89% yield (yield calculated on phosphorus atoms).

[0085] Main NMR data: .sup.1H NMR (500 MHz, CDCl.sub.3): 7.11-7.52 (m, 14H), 7.63 (d, J=7.7 Hz, 2H), 7.85 (s, .sup.1H), 7.91 (d, J=8.3 Hz, 2H), 7.98 (s, .sup.1H), 8.01 (d, J=8.3 Hz, 2H); .sup.13C NMR (125 MHz, CDCl.sub.3): 123.6, 123.9, 125.7, 125.9, 126.3 126.6, 127.1, 127.3, 127.8, 128.3, 128.4, 128.5, 129.8, 130.4, 130.7, 131.1, 131.2, 131.5, 132.37, 132.41, 133.9, 134.8, 137.9, 138.5, 145.5 (d, J=9.3 Hz), 146.0 (d, J=13.7 Hz); .sup.31P NMR (202 MHZ, CDCl.sub.3): 62.6.

INDUSTRIAL APPLICABILITY

[0086] The cyclic phosphate compounds containing a diaryl structural unit and derivatives thereof of the present disclosure have a wide range of applications as organophosphorus ligands in asymmetric catalysis.