Process for the synthesis of organic sulfates from dialkyl sulfate or pyrosulfate

Abstract

This invention discloses a method for preparing organic sulfates, characterized by the following steps: using dialkyl sulfate esters or pyrosulfates containing sulfate functional groups as sulfating reagents, and achieving the transformation of functional groups of alcoholic hydroxyl compounds or phenolic compounds through in-situ proton activation, thereby preparing the organic sulfate. This invention uses dialkyl sulfate esters as the source and enhances their electrophilicity through in-situ activation of sulfate ions, enabling nucleophilic attack by different hydroxyl compounds. This mechanism allows for the efficient synthesis of organic sulfates.

Description

Technical Field

[0001] This invention relates to the fields of organic chemistry and sulfation, and discloses a novel application of a new class of dialkyl sulfates or pyrosulfates as sulfation reagents. Background Technology

[0002] Organosulfate compounds are widely distributed in nature, including nucleosides, polypeptides, proteins, steroids, polysaccharides, and pheromones. They play important roles in biological functions such as signal transduction, hormone regulation, molecular recognition, and detoxification. Furthermore, post-sulfation treatment of natural drug molecules is a common drug modification technique. For example, sulfation of heparin and chondroitin yields heparin sulfate and chondroitin sulfate, enhancing their intermolecular interactions and protein-receptor binding. Of particular note is the discovery of avibactam sodium, the first antibiotic containing an organosulfate, which has spurred the gradual reporting of other novel β-lactamase inhibitors. Due to the crucial role of organosulfate compounds in various important biological processes, their synthesis has become a focus of considerable interest.

[0003] To date, the most common method for introducing sulfate groups into compounds is the nucleophilic addition reaction of hydroxyl or amino groups in the compound with sulfur trioxide (SO3)-organoamine complexes. This method has good universality but also significant limitations: it relies entirely on the nucleophilicity of the hydroxyl and amino functional groups in the substrate (Umesh R. Desai. Tetrahedron, 2010, 66, 2907-2918; Al an M. Jones. Chem. Commun., 2019, 55, 4319-4322), and sulfur trioxide is highly toxic and has poor biocompatibility. Other methods, such as esterification of hydroxyl-containing compounds with sulfuric acid and addition reactions of concentrated sulfuric acid with alkenes, are theoretically feasible; however, the weak nucleophilicity of sulfate ions imposes strict requirements on the substrate and demanding reaction conditions, limiting their practical application. Therefore, developing a novel sulfation reagent and a sulfation method with mild reaction conditions is of great importance. Summary of the Invention

[0004] To address the limitations of traditional sulfation substrates and the high toxicity of sulfation reagents, this invention discloses an organic sulfate and its preparation method.

[0005] A method for preparing an organic sulfate includes the following steps: using a dialkyl sulfate ester or pyrosulfate containing a sulfate functional group as a sulfating agent, and achieving in-situ activation by protons to convert the functional groups of hydroxyl compounds or phenolic compounds, thereby preparing the organic sulfate. The general molecular formulas of the dialkyl sulfate ester and pyrosulfate are as follows:

[0006]

[0007] R1 includes hydrocarbon groups with ≥C1 such as methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, etc.; M is a counter cation, including but not limited to Na, K, NBu4, NEt4, NHEt3, etc.

[0008] An organic sulfate having the following general molecular formula:

[0009]

[0010] R includes substituted hydrocarbon groups and substituted aromatic (hetero) groups. Substituents include ≥C1 hydrocarbon groups, aryl groups, alkoxy groups, alkylthio groups, silyl groups, boron groups, ester groups, amide groups, cyano groups, trifluoromethyl groups, aldehyde groups, nitro groups, alkenyl groups, alkynyl groups, azide groups, or halogen atoms. The number of substituents is one or more. M is a counter cation, including but not limited to Na, K, NBu4, NEt4, NHEt3, etc.

[0011] This invention utilizes dialkyl sulfates and pyrosulfates as sources, employing in-situ proton activation to act on various hydroxyl compound substrates. The dialkyl sulfates and pyrosulfates act as sulfate donors in the functional group transformation of organic compounds, resulting in the efficient synthesis of organic sulfates. The dialkyl persulfates used in this invention include dimethyl sulfate, diethyl sulfate, dipropyl sulfate, diisopropyl sulfate, dibutyl sulfate, etc. The applicable hydroxyl compounds include, but are not limited to, primary alcohols, secondary alcohols, tertiary alcohols, nitrogen-hydroxy compounds, phenols, sugars, etc. Detailed Implementation

[0012] The technical solution of the present invention will be specifically described below through specific embodiments. Unless otherwise specified, the components or devices in the following embodiments are all general standard parts or components known to those skilled in the art. Their structures and principles can be learned by those skilled in the art through technical manuals or conventional experimental methods.

[0013] General Instructions

[0014] The abbreviations used in the implementation examples have the following meanings: Me is methyl, Ph is phenyl, Bu is butyl, CH3CN is acetonitrile, DMS is dimethyl sulfate, DPS is diisopropyl sulfate, and NMR is nuclear magnetic resonance.

[0015] All anhydrous and oxygen-free experimental conditions involved in this invention were performed in accordance with Schlenk's technical standards. The solvents used were purified and dried using standard methods before use. All compounds used were commercially available or synthesized according to methods in existing literature, and were purified before use.

[0016] Traditional sulfation reactions have typically utilized the nucleophilicity of the starting material in an alkaline system to initiate an addition reaction with an active sulfur trioxide complex (electrophilic); or they have leveraged the weak nucleophilicity of the sulfate anion. The core of this invention lies in dialkyl sulfates, transforming them not merely into alkylating agents, but into important sulfate-functionalized reagents. This invention enhances the electrophilicity of dialkyl sulfates (using dimethyl sulfate as an example) through in-situ activation with acid. The general mechanism of the sulfation reaction is shown below:

[0017]

[0018] The structure of pyrosulfate is S2O7. 2- Containing the structural unit SO3, the essence of the above-mentioned dialkyl sulfate as a sulfating agent is the transfer of its SO3 functional group to the hydroxyl substrate. Therefore, based on the activation model of dialkyl sulfate, activating the sulfur atom of pyrosulfate under acidic conditions increases its electrophilicity. After attack by the hydroxyl nucleophile, the SO3 functional group can be introduced, realizing the sulfation reaction of hydroxyl compounds. The general mechanism is as follows:

[0019]

[0020] Example 1

[0021] This embodiment focuses on a method for preparing an organic sulfate compound using a hydroxyl compound (alkyl alcohol) as a substrate and a dialkyl sulfate ester as the sulfate source, the general formula of which is as follows:

[0022]

[0023] R includes substituted hydrocarbon groups and substituted aromatic (hetero) groups. Substituents include ≥C1 hydrocarbon groups, aryl, alkoxy, alkylthio, silyl, boronyl, ester, amide, cyano, trifluoromethyl, aldehyde, nitro, alkenyl, alkynyl, azide, or halogen atoms, and there may be one or more substituents. R1 includes ≥C1 hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, etc.

[0024] Ammonium salts include triethylamine, diethylamine, N,N-diisopropylethylamine, aniline, imidazole, pyridine, ammonium chloride, ammonium fluoroborate, ammonium hexafluorophosphate, ammonium sulfate, ammonium persulfate, tetrabutylammonium acetate, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetrabutylammonium nitrate, tetrabutylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hydrogen sulfate, tetraethyl-p-toluenesulfonate, tetraethylammonium iodide, tetraethylammonium perchlorate, ammonium iodide, di-tert-butyltetrabutylammonium phosphate, tetramethylammonium hydrogen sulfate, tetrapropylammonium bromide, etc.

[0025] Example 2

[0026] This embodiment focuses on a method for preparing an organic sulfate compound using phenolic compounds as substrates and pyrosulfate as the sulfate source, the general formula of which is as follows:

[0027]

[0028] Where R 1 Including ≥C1 hydrocarbon, aryl, alkoxy, alkylthio, silyl, boron, ester, amide, cyano, trifluoromethyl, aldehyde, nitro, alkenyl, alkynyl, or halogen atoms, and substituents R. 1 The number of bases is 1 to 5; M is the counter cation; base is an organic or inorganic base, including LiHCO3, Li2CO3, Li3PO4, LiH2PO4, Li2HPO4, LiHC2O4, Li2C2O4, CH3COOLi, HCOOLi, LiOH, MeOLi, t-BuOLi, NaHCO3, Na2CO3, Na3PO4, NaH2PO4, Na2HPO4, NaHC2O4, Na2C2O4, CH3COONa, HCOONa, NaO H, MeONa, t-BuONa, KHCO3, K2CO3, K3PO4, KH2PO4, K2HPO4, KHC2O4, K2C2O4, CH3COOK, HCOOK, KOH, KOLi, t-BuOK, NH4HCO3, (NH4)2CO3, (NH4)3PO4, (NH4)H2PO4, (NH4)2HPO4, NH4HC2O4, (NH4)2C2O4, ammonia, triethylamine, diisopropylamine, trimethylamine, piperidine, pyridine, and ammonium salts are the same as in Example 1.

[0029] Example 3

[0030] This embodiment focuses on a method for preparing an organosulfate compound using an N-hydroxy compound as a substrate and pyrosulfate as the sulfate source, the general formula of which is as follows:

[0031]

[0032] Wherein, R1 includes ≥C1 hydrocarbon groups, aryl groups, alkoxy groups, alkylthio groups, silyl groups, boron groups, ester groups, amide groups, cyano groups, trifluoromethyl groups, aldehyde groups, nitro groups, alkenyl groups, alkynyl groups, or heteroatoms; R2 includes ≥C1 hydrocarbon groups, aryl groups, alkoxy groups, alkylthio groups, silyl groups, boron groups, ester groups, amide groups, cyano groups, trifluoromethyl groups, aldehyde groups, nitro groups, alkenyl groups, alkynyl groups, or heteroatoms; M is a counter cation; base and ammonium salt are the same as in Example 2.

[0033] Experimental Example 1: Preparation of N-(3-hydroxypropyl)phthalimide tetrabutylammonium sulfate

[0034]

[0035] N-(3-hydroxypropyl)phthalimide (0.2 mmol), dimethyl sulfate (0.24 mmol), and tetrabutylammonium hydrogen sulfate (0.24 mmol) were added sequentially to a 4 mL reaction flask. After the additions were complete, the 4 mL reaction flask was sealed and evacuated, then purged with argon gas. This process was repeated three times. Finally, 1 mL of acetonitrile was added to the flask, and the mixture was heated to 80°C and reacted for 12 hours. After the reaction was complete, the organic phase was concentrated and subjected to column chromatography. N-(3-hydroxypropyl)phthalimide tetrabutylammonium sulfate (84.3 mg, 80%) was separated using a dichloromethane to methanol eluent at a volume ratio of 20:1. 1 H NMR(400MHz,Chloroform-d,298K,δ):7.76-7.72(m,2H),7.67-7.64(m,2H),4.03(t,J=6.5Hz,2H),3.73(t,J=7.5H z,2H),3.27-3.22(m,8H),1.97(p,J=6.7Hz,2H),1.65-1.58(m,8H),1.38(h,J=7.4Hz,8H),0.93(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 168.2, 133.9, 132.1, 123.1, 64.6, 58.6, 35.5, 28.8, 23.9, 19.7, 13.7.

[0036] Experimental Example 2: Preparation of p-fluorophenylethanol tetrabutylammonium sulfate

[0037]

[0038] The experimental procedure is shown in Example 1, using tetrabutylammonium fluorophenylethanol (65.6 mg, 71%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 7.13 (dd, J=8.4, 5.6Hz, 2H), 6.85 (t, J=8.7Hz, 2H), 4.10 (t, J=7.4Hz, 2H ),3.17-3.13(m,8H),2.88(t,J=7.4Hz,2H),1.57-1.49(m,8H),1.32(h,J=7.3Hz,8H),0.90(t,J=7.4Hz,12H). 13C NMR (101MHz, Chloroform-d, 298K, δ): 161.3 (d, J = 243.2Hz), 134.4 (d, J = 3.2Hz ), 130.4 (d, J = 7.8Hz), 114.8 (d, J = 21.1Hz), 67.3, 58.5, 35.1, 23.8, 19.6, 13.6. 19 F NMR (376MHz, Chloroform-d, 298K, δ): -117.58.

[0039] Experimental Example 3: Preparation of 3-bromophenylethanol tetrabutylammonium sulfate

[0040]

[0041] The experimental procedure is shown in Example 1, 3-bromophenylethanol tetrabutylammonium sulfate (69.9 mg, 67%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 7.31 (s, 1H), 7.22 (d, J = 7.8Hz, 1H), 7.11 (d, J = 7.8Hz, 1H), 7.05 (t, J = 7.7Hz, 1H), 4.11 (t,J=7.2Hz,2H),3.16-3.12(m,8H),2.88(t,J=7.2Hz,2H),1.56-1.48(m,8H),1.31(h,J=7.3Hz,8H),0.89(t,J=7.4Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 141.2, 131.8, 129.8, 129.1, 127.7, 122.0, 66.8, 58.4, 35.6, 23.8, 19.6, 13.6.

[0042] Experimental Example 4: Preparation of 1-naphthylethanol tetrabutylammonium sulfate

[0043]

[0044] The experimental procedure is shown in Example 1. The amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and 1-naphthylethanol tetrabutylammonium sulfate (79.9 mg, 81%) was added. 1H NMR (400MHz, Chloroform-d, 298K, δ): 8.13 (d, J = 8.3Hz, 1H), 7.81 (d, J = 7.9Hz, 1H), 7.69 (d, J = 8.0Hz, 1H), 7.50-7.41 (m, 3H), 7.36 (t, J = 7 .6Hz,1H),4.37(t,J=7.6Hz,2H),3.50(t,J=7.5Hz,2H),3.24-3.19(m,8H),1.63-1.55(m,8H),1.44-1.35(m,8H),0.96(t,J=7.8Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 134.9, 133.9, 132.4, 128.7, 126.9, 126.0, 125.7, 125.5, 124.2, 67.0, 58.8, 33.3, 24.1, 19.8, 13.8.

[0045] Experimental Example 5: Preparation of 4-Nitrophenylethanol Tetrabutylammonium Sulfate

[0046]

[0047] The experimental procedure is shown in Example 1, 4-nitrophenylethanol tetrabutylammonium sulfate (77.9 mg, 80%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 8.06 (d, J = 8.7Hz, 2H), 7.42 (d, J = 8.7Hz, 2H), 4.23 (t, J = 6.8Hz, 2H), 3.22-3.18(m,8H),3.07(t,J=6.8Hz,2H),1.63-1.55(m,8H),1.37(h,J=7.3Hz,8H),0.94(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 147.3, 146.4, 130.0, 123.4, 66.4, 58.7, 35.8, 23.9, 19.7, 13.7.

[0048] Experimental Example 6: Preparation of 4-cyanophenylethanol tetrabutylammonium sulfate

[0049]

[0050] The experimental procedure is shown in Example 1, 4-cyanophenylethanol tetrabutylammonium sulfate (67.5 mg, 72%). 1H NMR (400MHz, Chloroform-d, 298K, δ): 7.53 (d, J = 8.2Hz, 2H), 7.39 (d, J = 8.2Hz, 2H), 4.25 (t, J = 6.9Hz, 2H), 3.25-3.21(m,8H),3.06(t,J=6.9Hz,2H),1.66-1.58(m,8H),1.41(h,J=7.4Hz,8H),0.98(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 145.0, 132.1, 130.1, 119.4, 109.9, 66.7, 58.9, 36.1, 24.1, 19.8, 13.8.

[0051] Experimental Example 7: Preparation of 4-tert-butylphenylethanol tetrabutylammonium sulfate

[0052]

[0053] The experimental procedure is shown in Example 1, 4-tert-butylphenylethanol tetrabutylammonium sulfate (81.3 mg, 81%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 7.23 (d, J = 8.3 Hz, 2H), 7.12 (d, J = 8.3 Hz, 2H), 4.14 (t, J = 7.8 Hz, 2H), 3.22-3 .18(m,8H),2.92(t,J=7.8Hz,2H),1.60-1.52(m,8H),1.36(h,J=7.4Hz,8H),1.24(s,9H),0.92(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 148.8, 135.4, 128.6, 125.1, 67.5, 58.5, 35.5, 34.3, 31.4, 23.9, 19.6, 13.6.

[0054] Experimental Example 8: Preparation of 4-methoxyphenylethanol tetrabutylammonium sulfate

[0055]

[0056] The experimental procedure is shown in Example 1, 4-methoxyphenylethanol tetrabutylammonium sulfate (77.7 mg, 82%). 1H NMR (400MHz, Chloroform-d, 298K, δ): 7.13 (d, J = 8.5 Hz, 2H), 6.77 (d, J = 7.5 Hz, 2H), 4.15 (t, J = 7.6 Hz, 2H), 3.74 (s,3H),3.24-3.19(m,8H),2.92(t,J=7.6Hz,2H),1.63-1.55(m,8H),1.44-1.34(m,8H),0.96(t,J=7.1Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 158.0, 130.8, 130.0, 113.8, 67.8, 58.7, 55.3, 35.3, 24.0, 19.8, 13.8.

[0057] Experimental Example 9: Preparation of 2,5-dichlorophenylethanol tetrabutylammonium sulfate

[0058]

[0059] The experimental procedure is shown in Example 1, 2,5-dichlorophenylethanol tetrabutylammonium sulfate (81.8 mg, 80%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 7.20 (d, J = 8.0Hz, 2H), 7.05-7.01 (m, 1H), 4.08-4.04 (m, 2H), 3. 32-3.28(m,2H),3.24-3.20(m,8H),1.62-1.54(m,8H),1.36(h,J=7.4Hz,8H),0.92(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 136.0, 134.1, 128.1, 128.1, 63.8, 58.5, 31.8, 23.9, 19.7, 13.7.

[0060] Experimental Example: Preparation of Tetrabutylammonium Trimethylphenylethanol

[0061]

[0062] The experimental procedure is shown in Example 1. The amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and the content of trimethylphenylethanol tetrabutylammonium sulfate (87.2 mg, 90%) was increased. 1H NMR(400MHz,Chloroform-d,298K,δ):6.77(s,2H),4.01-3.96(m,2H),3.25-3.21(m,8H),3.03-2.99 (m,2H),2.29(s,6H),2.19(s,3H),1.64-1.56(m,8H),1.39(h,J=7.4Hz,8H),0.96(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 136.9, 135.4, 131.7, 128.8, 65.3, 58.7, 30.0, 24.0, 20.8, 19.9, 19.7, 13.7.

[0063] Experimental Example: Preparation of Undecylpentanol Tetrabutylammonium Sulfate

[0064]

[0065] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and the amount of allyl tetrabutylammonium sulfate (75.3 mg, 92%) was added. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 5.79-5.69 (m, 1H), 4.96-4.84 (m, 2H), 3.93 (t, J = 6.8Hz, 2H), 3.22-3.18 ( m,8H),2.10-2.03(m,2H),1.70-1.63(m,2H),1.60-1.52(m,8H),1.36(h,J=7.4Hz,8H),0.92(t,J=7.4Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 138.2, 114.5, 66.5, 58.5, 30.1, 28.9, 23.9, 19.6, 13.6.

[0066] Experimental Example: Preparation of Tetrabutylammonium Dodecapentylenesulfonate

[0067]

[0068] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and tetrabutylammonium ethynyl ammonium sulfate (70.6 mg, 87%) was added. 1H NMR (400MHz, Chloroform-d, 298K, δ): 4.04 (t, J = 6.3 Hz, 2H), 3.26-3.22 (m, 8H), 2.28 (td, J = 7. 4,2.7Hz,2H),1.89-1.82(m,3H),1.65-1.57(m,8H),1.45-1.36(m,8H),0.97(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 84.3, 68.3, 65.8, 58.7, 28.9, 24.0, 19.8, 15.3, 13.7.

[0069] Experimental Example XIII: Preparation of 3-Phenylen-2-propyn-1-ol Tetrabutylammonium Sulfate

[0070]

[0071] The experimental procedure is shown in Example 1. Dimethyl sulfate was replaced with diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 3-phenyl-2-propyn-1-ol tetrabutylammonium sulfate (57.2 mg, 63%) was added. 1 H NMR(400MHz,Chloroform-d,298K,δ):7.35-7.32(m,2H),7.26-7.24(m,3H),4.78(s,2H) ),3.21-3.17(m,8H),1.60-1.52(m,8H),1.36(h,J=7.4Hz,8H),0.92(t,J=7.4Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 131.6, 128.4, 128.3, 122.7, 85.5, 85.1, 58.5, 55.5, 23.8, 19.6, 13.6.

[0072] Experimental Example 14: Preparation of Tetrabutylammonium 4-Vinylbenzyl alcohol

[0073]

[0074] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 4-vinylbenzyl alcohol tetrabutylammonium sulfate (50.3 mg, 55%) was added. 1H NMR (400MHz, Chloroform-d, 298K, δ): 7.36-7.31 (m, 4H), 6.67 (dd, J=17.6, 10.9Hz, 1H), 5.70 (d, J=17.6Hz, 1H), 5.20 (d,J=10.8Hz,1H),5.02(s,2H),3.19-3.15(m,8H),1.59-1.51(m,8H),1.36(h,J=7.3Hz,8H),0.94(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 137.5, 136.8, 136.7, 128.4, 126.0, 113.7, 68.7, 58.6, 24.0, 19.8, 13.8.

[0075] Experimental Example 15: Preparation of 4-Borate Pinaryl Ester-Based Benzyl Alcohol Tetrabutylammonium Sulfate

[0076]

[0077] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 4-boronic acid pinacol ester benzyl alcohol tetrabutylammonium sulfate (88.1 mg, 79%) was added. 1 H NMR(400MHz,Chloroform-d,298K,δ):7.72(d,J=7.7Hz,2H),7.38(d,J=7.7Hz,2H),5.05( s,2H),3.19-3.14(m,8H),1.58-1.50(m,8H),1.40-1.31(m,20H),0.94(t,J=7.3Hz,12H). 13 CNMR(101MHz,Chloroform-d,298K,δ):141.0,134.7,127.1,83.8,68.8,58.6,25.0,23.9,19.7,13.8.

[0078] Experimental Example 16: Preparation of 4-formylbenzyl alcohol tetrabutylammonium sulfate

[0079]

[0080] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 4-formylbenzyl alcohol tetrabutylammonium sulfate (64.1 mg, 70%) was added. 1H NMR (400MHz, Chloroform-d, 298K, δ): 9.96 (s, 1H), 7.79 (d, J = 8.2Hz, 2H), 7.57 (d, J = 7.9Hz, 2H) ,5.12(s,2H),3.24-3.19(m,8H),1.63-1.55(m,8H),1.42-1.33(m,8H),0.94(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 192.3, 145.2, 135.6, 129.7, 128.0, 68.1, 58.8, 24.0, 19.8, 13.7.

[0081] Experimental Example 17: Preparation of 4-methylsulfonylbenzyl alcohol tetrabutylammonium sulfate

[0082]

[0083] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 4-methyl sulfone benzyl alcohol tetrabutylammonium sulfate (73.2 mg, 72%) was added. 1 H NMR(400MHz,Chloroform-d,298K,δ):7.77(d,J=8.4Hz,2H),7.55(d,J=8.1Hz,2H),5.06(s,2H), 3.16-3.12(m,8H),2.95(s,3H),1.57-1.49(m,8H),1.32(h,J=7.4Hz,8H),0.88(t,J=7.4Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 144.7, 139.0, 128.0, 127.0, 67.5, 58.5, 44.5, 23.8, 19.6, 13.6.

[0084] Experimental Example: Preparation of Octathathiophene 3-ethanol tetrabutylammonium sulfate

[0085]

[0086] The experimental procedure is shown in Example 1, using thiophene 3-ethanol tetrabutylammonium sulfate (71.8 mg, 80%). 1H NMR (400MHz, Chloroform-d, 298K, δ): 7.15 (dd, J=4.9, 3.0Hz, 1H), 7.02-7.01 (m, 1H), 6.93 (dd, J=4.9, 1.3Hz, 1H), 4.17 (t ,J=7.3Hz,2H),3.20-3.16(m,8H),2.96(t,J=7.3Hz,2H),1.60-1.52(m,8H),1.36(h,J=7.3Hz,8H),0.93(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 139.0, 128.6, 124.9, 121.1, 66.7, 58.6, 30.5, 23.9, 19.7, 13.7.

[0087] Experimental Example 19: Preparation of Tetrabutylammonium Trichloroethanol

[0088]

[0089] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and the amount of trichloroethanol tetrabutylammonium sulfate (31.9 mg, 34%) was increased. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 4.49 (s, 2H), 3.22-3.17 (m, 8H), 1.57 (p, J = 7.7Hz, 8H), 1.37 (h, J = 7.3Hz, 8H), 0.93 (t, J = 7.3Hz, 12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 96.2, 77.8, 23.9, 19.7, 13.6.

[0090] Experiment 20: Preparation of 4-phenyl-2-butanol tetrabutylammonium sulfate

[0091]

[0092] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 4-phenyl-2-butanol tetrabutylammonium sulfate (79.3 mg, 84%) was added. 1H NMR(400MHz,Chloroform-d,298K,δ):7.23-7.17(m,4H),7.12-7.09(m,1H),4.52(h, J=6.3Hz,1H),3.27-3.22(m,8H),2.80(td,J=16.3,11.4,5.3Hz,1H),2.68(td,J=13.6 ,12.6,5.5Hz,1H),1.95(tt,J=12.3,6.2Hz,1H),1.76(tt,J=11.6,5.3Hz,1H),1.61( p,J=7.8Hz,8H),1.41(h,J=7.3Hz,8H),1.33(d,J=6.2Hz,3H),0.96(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 143.0, 128.5, 128.2, 125.5, 73.9, 58.7, 32.0, 24.0, 21.2, 19.8, 13.7.

[0093] Experimental Example 21: Preparation of Methyl 3-hydroxyhexanoate Tetrabutylammonium Sulfate

[0094]

[0095] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and methyl 3-hydroxyhexanoate tetrabutylammonium sulfate (38.2 mg, 41%) was added. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 4.67-4.61 (m, 1H), 3.60 (s, 3H), 3.26-3.21 (m, 8H), 3.09 (dd, J=15.3, 4.4Hz, 1H ),2.50(dd,J=15.3,9.0Hz,1H),1.64-1.47(m,12H),1.44-1.35(m,8H),0.96(t,J=7.3Hz,12H),0.85(t,J=7.0Hz,3H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 172.1, 73.6, 58.6, 51.4, 40.2, 37.2, 24.0, 19.7, 18.5, 14.1, 13.7.

[0096] Experiment 22: Preparation of 2-Indanol Tetrabutylammonium Sulfate

[0097]

[0098] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 2-indanol tetrabutylammonium sulfate (66.5 mg, 73%) was added. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 7.17-7.13 (m, 2H), 7.11-7.08 (m, 2H), 5.25 (p, J = 5.2Hz, 1H), 3.2 5-3.23(m,4H),3.20-3.15(m,8H),1.56(p,J=7.6Hz,8H),1.38(h,J=7.4Hz,8H),0.96(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 141.5, 126.3, 124.6, 78.0, 40.4, 24.0, 19.7, 13.8.

[0099] Experimental Example 23: Preparation of DL-Menthol Tetrabutylammonium Sulfate

[0100]

[0101] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and DL-menthol tetrabutylammonium sulfate (68.8 mg, 72%) was added. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 4.13 (td, J=10.7, 4.4Hz, 1H), 3.29-3.25 (m, 8H), 2.52 (d, J=12.5Hz, 1H), 2.35 (p, J=7 .1Hz,1H),1.67-1.59(m,10H),1.43(h,J=7.4Hz,9H),1.26-1.20(m,1H),0.98(t,J=7.3Hz,15H),0.84(q,J=6.9,6.3Hz,9H). 13 CNMR(101MHz,Chloroform-d,298K,δ):77.6,58.8,48.3,42.3,34.7,31.7,25.3,24.1,23.3,22.3,21.4,19.8,16.2,13.8.

[0102] Experiment 24: Preparation of 2-adamantanoic acid tetrabutylammonium sulfate

[0103]

[0104] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 2-adamantanoic acid tetrabutylammonium sulfate (88.9 mg, 94%) was added. 1 H NMR(400MHz,Chloroform-d,298K,δ):4.51-4.49(m,1H),3.29-3.24(m,8H),2.22(s,2H),2.16 (s,2H),1.79-1.70(m,6H),1.67-1.58(m,10H),1.42(h,J=7.0Hz,10H),0.98(t,J=7.3Hz,12H). 13 CNMR(101MHz,Chloroform-d,298K,δ):80.3,37.8,36.8,32.7,31.7,27.5,27.3,24.1,19.8,13.8.

[0105] Experimental Example: Preparation of Tetrabutylammonium Pentacyclic Dodecayl Alcohol Sulfate

[0106]

[0107] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and the amount of cyclododecyl tetrabutylammonium sulfate (84.8 mg, 84%) was increased. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 4.54-4.48 (m, 1H), 3.31-3.27 (m, 8H), 1.74 (ddd, J=24.1, 11.8, 5.8Hz, 4H), 1.67-1.62 (m, 8H), 1.45 (p, J=7.4Hz, 13H), 1.30 (td, J=21.5, 19.4, 12.2Hz, 14H), 0.99 (d, J=7.3Hz, 12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 76.5, 59.0, 29.7, 25.1, 24.7, 24.2, 23.4, 23.3, 20.6, 19.9, 13.8.

[0108] Experiment 26: Preparation of N-Tosyl-4-piperidinol tetrabutylammonium sulfate

[0109]

[0110] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and N-Tosyl-4-piperidinol tetrabutylammonium sulfate (92.2 mg, 80%) was added. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 7.55 (d, J=7.9Hz, 2H), 7.25 (d, J=8.1Hz, 2H), 4.40 (p, J=5.0Hz, 1H), 3.19-3.15 (m, 8H), 3.13-3 .07(m,2H),3.02-2.97(m,2H),2.38(s,3H),1.92(q,J=5.4Hz,4H),1.60-1.52(m,8H),1.35(h,J=7.4Hz,8H),0.92(t,J=7.3Hz,12H). 13 C NMR (101 MHz, Chloroform-d, 298 K, δ): 143.6, 133.2, 129.7, 127.6, 70.6, 58.7, 43.2, 31.0, 23.9, 21.6, 19.7, 13.7. Example 27: Preparation of DL-pantolactone tetrabutylammonium sulfate.

[0111]

[0112] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and DL-pantolactone tetrabutylammonium sulfate (29.8 mg, 33%) was added. 1 H NMR(400MHz,Chloroform-d,298K,δ):4.87(s,1H),3.97-3.92(m,2H),3.30-3.26(m,8H),1 .69-1.61(m,8H),1.43(h,J=7.4Hz,8H),1.34(s,3H),1.12(s,3H),0.99(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 174.9, 79.1, 76.5, 58.8, 40.7, 24.1, 23.2, 19.8, 19.7, 13.8.

[0113] Experimental Example 28: Preparation of 4-chloro-6,7-dihydro-5H-cyclopentano[B]pyridine-7-ol tetrabutylammonium sulfate

[0114]

[0115] The experimental procedure is shown in Example 1. Dimethyl sulfate was replaced with diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium hydrogen sulfate was increased to 0.4 mmol, and 4-chloro-6,7-dihydro-5H-cyclopenta[B]pyridine-7-ol tetrabutylammonium sulfate (39.2 mg, 40%) was added. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 8.30 (d, J = 5.3Hz, 1H), 7.15 (d, J = 5.3Hz, 1H), 5.78 (dd, J = 7.0, 4.0Hz, 1H), 3.29-3.24 (m, 8H ),3.13-3.05(m,1H),2.88-2.82(m,1H),2.66-2.47(m,2H),1.63(q,J=7.9Hz,8H),1.39(q,J=7.4Hz,8H),0.95(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 163.6, 149.0, 141.7, 137.2, 123.3, 80.3, 30.5, 27.3, 24.0, 19.8, 13.8.

[0116] Experiment Example 29: Preparation of Icaridin Tetrabutylammonium Sulfate

[0117]

[0118] The experimental procedure is shown in Example 1, using icostigmine tetrabutylammonium sulfate (66.0 mg, 60%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 4.66 (h, J = 6.2Hz, 1H), 4.32-4.29 (m, 1H), 4.03-3.90 (m, 3H), 3.27-3.23 (m, 8H), 2.81 (t, J = 13.0Hz, 1H ),2.04-1.86(m,2H),1.66-1.49(m,15H),1.40(h,J=7.4Hz,9H),1.15(t,J=6.2Hz,3H),0.97(t,J=7.3Hz,12H),0.85(td,J=7.4,3.1Hz,3H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 155.5, 72.8, 64.9, 58.7, 48.3, 39.2, 29.7, 29.1, 28.2, 25.6, 24.0, 19.9, 19.8, 19.1, 13.8, 9.84, 9.81.

[0119] Experiment 30: Preparation of Aloe-emodin Tetrabutylammonium Sulfate

[0120]

[0121] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and the amount of aloe-emodin tetrabutylammonium sulfate (73.4 mg, 62%) was added. 1 H NMR(400MHz,Chloroform-d,298K,δ):12.01(s,1H),11.95(s,1H),7.74-7.71(m,2H),7.64-7.60(m,1H),7.34(s,1H),7.2 2(dd,J=8.4,1.2Hz,1H),5.10(s,2H),3.27-3.22(m,8H),1.66-1.58(m,8H),1.38(h,J=7.3Hz,8H),0.93(t,J=7.4Hz,12H). 13 C NMR(101MHz,Chloroform-d,298K,δ):192.6,181.6,162.8,162.5,149.3,137.1,13 3.6,133.3,124.6,122.4,119.9,118.6,115.8,114.7,67.4,58.7,23.9,19.7,13.7.

[0122] Experimental Example 31: Preparation of Osipemid Tetrabutylammonium Sulfate

[0123]

[0124] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and osepirimicarb tetrabutylammonium sulfate (111.9 mg, 80%) was added. 1H NMR(400MHz,Chloroform-d,298K,δ):7.30-7.26(m,2H),7.22-7.18(m,3H),7. 14-7.04(m,5H),6.68(d,J=8.8Hz,2H),6.44(d,J=8.8Hz,2H),4.18(t,J=5.1Hz ,2H),3.99(t,J=5.1Hz,2H),3.33(t,J=7.4Hz,2H),3.16-3.12(m,8H),2.83(t, J=7.5Hz,2H),1.55-1.47(m,8H),1.30(h,J=7.4Hz,8H),0.86(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 157.1, 142.9, 141.7, 140.9, 135.1, 134.8, 131.6, 129. 5,129.4,128.3,128.2,126.9,126.6,113.5,66.9,65.2,58.6,42.9,38.6,23.9,19.7,13.7.

[0125] Experimental Example 30: Preparation of Tetrabutylammonium Testosterone

[0126]

[0127] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and the amount of tetrabutylammonium testosterone (107.1 mg, 88%) was increased. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 5.70 (s, 1H), 4.28 (t, J = 8.5Hz, 1H), 3.30 -3.25(m,8H),2.45-2.16(m,5H),2.10-2.01(m,2H),1.84-1.76(m,2H),1.69-1. 60(m,9H),1.57-1.49(m,2H),1.44(q,J=7.4Hz,9H),1.40-1.37(m,1H),1.32-1. 20(m,3H),1.17(s,3H),1.00(t,J=7.3Hz,12H),0.94-0.88(m,2H),0.84(s,3H). 13C NMR(101MHz,Chloroform-d,298K,δ):199.8,171.9,123.8,85.5,58.9,54.0,50.3,42.7, 38.8,36.6,35.8,35.7,34.1,33.0,31.7,28.4,24.1,23.5,20.7,19.9,17.5,13.8,11.8.

[0128] Experimental Example 33: Preparation of Diosgenin Tetrabutylammonium Sulfate

[0129]

[0130] The experimental procedure is shown in Example 1, diosgenin tetrabutylammonium sulfate (132.4 mg, 90%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 5.28 (s, 1H), 4.35 (q, J = 7.4Hz, 1H), 4.19-4.11 (m, 1H), 3.42 (d, J = 10. 8Hz,1H),3.32(t,J=10.9Hz,1H),3.25-3.21(m,8H),2.55(d,J=16.4Hz,1H),2.38(s,1H),2.31-2.25(m,1H), 2.08(d,J=11.0Hz,1H),1.98-1.89(m,2H),1.82(t,J=6.9Hz,1H),1.76-1.67(m,2H),1.63-1.53(m,14H),1.5 1-1.35(m,11H),1.22(dt,J=12.1,6.6Hz,1H),1.16-1.02(m,3H),0.97-0.91(m,19H),0.74(d,J=6.1Hz,6H). 13 C NMR(101MHz,Chloroform-d,298K,δ):140.9,121.4,109.3,80.9,66.8,62.1,58.6,56.5,50.0,41.6,40.3,39 .8,39.5,37.3,36.7,32.1,31.9,31.4,31.4,30.3,29.1,28.8,24.0,20.8,19.8,19.4,17.2,16.3,14.6,13.8.

[0131] Experiment 34: Preparation of Tetrabutylammonium Cholesterol Sulfate

[0132]

[0133] The experimental procedure is shown in Example 1. The dimethyl sulfate was changed to diisopropyl sulfate (1.2 equiv), the amount of tetrabutylammonium bisulfate was increased to 0.4 mmol, and the amount of tetrabutylammonium cholesterol (69.3 mg, 49%) was increased. 1 H NMR(400MHz,Chloroform-d,298K,δ):5.31(s,1H),4.23-4.15(m,1H),3.28-3.24( m,8H),2.57(d,J=15.9Hz,1H),2.32(t,J=12.6Hz,1H),2.13-2.09(m,2H),2.00-1.8 8(m,2H),1.84-1.75(m,2H),1.66-1.58(m,9H),1.53-1.39(m,12H),1.37-1.30(m, 3H),1.15-0.97(m,25H),0.88(d,J=6.4Hz,4H),0.84(d,J=6.6Hz,6H),0.64(s,3H). 13 C NMR(101MHz,Chloroform-d,298K,δ):141.0,121.7,58.8,56.8,56.2,50.2,42.4,39.9,39.6,37.4,36.6,3 6.3,35.9,32.0,31.97,29.2,28.3,28.1,24.4,24.1,23.9,22.9,22.7,21.1,19.8,19.5,18.8,13.8,12.0.

[0134] Example 35: Preparation of the sugar derivative 1-35-tetrabutylammonium sulfate

[0135]

[0136] The experimental procedure is shown in Example 1, using the sugar derivative 1-35 tetrabutylammonium sulfate (12.0 mg, 38%). 1H NMR (600MHz, Chloroform-d, 298K): δ8.03(d,J=8.3Hz,2H),7.55–7.19(m,13H),5.23(d,J=12. 3Hz,1H),5.05(q,J=12.2Hz,2H),4.91(dd,J=12.0,2.1Hz,1H),4.79–4.60(m,4H),4.51(t,J=9 .6Hz,1H),4.04(t,J=8.8Hz,1H),3.92(td,J=10.0,3.6Hz,1H),3.69–3.63(m,1H),3.30(s,3H) ,3.25–3.19(m,8H),1.61(p,J=7.8Hz,8H),1.40(h,J=7.1Hz,8H),1.03–0.90(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ166.6,156.1,139.6,136.6,132.8,130.8,129.7,128.6,128.4,128 .2,128.1,127.2,98.5,78.3,76.6,74.4,69.4,66.8,64.9,58.8,55.0,54.5,29.8,24.1,19.8,13.8,1.2.

[0137] Example 36: Preparation of the sugar derivative 1-36 tetrabutylammonium sulfate

[0138]

[0139] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-36 tetrabutylammonium sulfate (26.0 mg, 81%) was used. 1H NMR(600MHz,Chloroform-d,298K): δ7.42–7.21(m,20H),4.99(d,J=11.2Hz,1H),4.89(m,J=16.2,10.6Hz ,2H),4.83–4.77(m,2H),4.71(d,J=12.3Hz,1H),4.66(d,J=12.0Hz,1H),4.54(d,J=1.8Hz,1H),4.42(dd,J =10.8,3.5Hz,1H),4.23(dd,J=10.9,2.1Hz,1H),4.04(t,J=9.3Hz,1H),3.94–3.86(m,1H),3.74(t,J=9.5 Hz,1H),3.53(dd,J=9.7,3.7Hz,1H),3.29–3.17(m,8H),1.61(m,8H),1.42(h,J=7.4Hz,8H),0.98(t,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ139.4,138.7,138.4,137.4,128.8,128.5,128.4,128.3,128.3,128.0,1 27.8,127.7,127.6,127.4,95.4,82.1,79.8,77.8,75.5,75.1,73.1,70.0,68.8,65.4,58.8,24.0,19.8,13.8.

[0140] Example 37: Preparation of the sugar derivative 1-37 tetrabutylammonium sulfate

[0141]

[0142] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-37 tetrabutylammonium sulfate (26.0 mg, 81%) was used. 1H NMR (500MHz, Chloroform-d, 298K): δ7.45(d,J=8.1Hz,2H),7.40–7.20(m,15H),7.10(d,J=7.9Hz,2H),4.94(d,J=10.1Hz,1H),4.91(d ,J=11.1Hz,1H),4.85(d,J=11.1Hz,1H),4.80(d,J=10.3Hz,1H),4.76(d,J=10.0Hz,1H),4.69(d,J=10.2Hz,1H),4.60(d,J=9.8Hz,1H) ,4.40(dd,J=10.8,3.9Hz,1H),4.35(dd,J=10.8,2.1Hz,1H),3.73(t,J=9.3Hz,1H),3.67(t,J=8.9Hz,1H),3.53(ddd,J=9.5,3.9,2.1H z,1H),3.40(t,J=8.5Hz,1H),3.30–3.23(m,8H),2.31(s,3H),1.65–1.59(m,8H),1.46–1.37(h,J=7.3Hz,8H),0.98(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ138.8,138.3,138.2,137.5,131.7,130.5,129.9,128.8,128.5,128.4,128.3,1 27.9,127.8,127.7,127.6,88.0,86.7,80.8,78.2,77.6,75.7,75.4,75.2,65.4,58.9,24.1,21.2,19.8,13.8,13.8.

[0143] Example 38: Preparation of 1-38 Tetrabutylammonium Sulfate Derivative

[0144]

[0145] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-38 tetrabutylammonium sulfate (18.0 mg, 56%) was used. 1H NMR (500MHz, Chloroform-d, 298K): δ8.24(d,J=7.0Hz,1H),7.52–7.37(m,7H),7.30(dd,J=8.3,6.7 Hz,2H),7.23(d,J=7.4Hz,1H),7.05(d,J=7.8Hz,2H),5.62(s,1H),5.38(d,J=2.6Hz,1H),5.35(t,J =3.0Hz,1H),4.91(t,J=3.2Hz,1H),4.85(m,2H),4.48(t,J=3.4Hz,1H),3.80(s,2H),3.18(m,J=8.4 Hz, 8H), 2.28 (s, 3H), 1.61–1.50 (m, 8H), 1.44–1.31 (dq, J=14.2, 6.9Hz, 8H), 0.94 (t, J=7.3Hz, 12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ169.6,166.0,138.2,137.4,132.9,132.2,132.0,130.8,130.1,12 9.7,128.3,127.7,127.5,86.2,74.0,72.7,71.2,69.8,68.9,58.9,54.4,52.1,24.1,21.2,19.8,13.8.

[0146] Example 39: Preparation of the sugar derivative 1-39 tetrabutylammonium sulfate

[0147]

[0148] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-39 tetrabutylammonium sulfate (22.0 mg, 69%) was used. 1H NMR (500MHz, Chloroform-d, 298K): δ8.24(d,J=7.0Hz,1H),7.52–7.37(m,7H),7.30(dd,J=8.3,6 .7Hz,2H),7.23(d,J=7.4Hz,1H),7.05(d,J=7.8Hz,2H),5.62(s,1H),5.38(d,J=2.6Hz,1H),5.35( t,J=3.0Hz,1H),4.91(t,J=3.2Hz,1H),4.85(m,2H),4.48(t,J=3.4Hz,1H),3.80(s,2H),3.18(m,J =8.4Hz,8H),2.28(s,3H),1.61–1.50(m,8H),1.44–1.31(h,J=7.4Hz,8H),0.94(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ171.8,166.0,137.9,137.6,133.2,132.8,132.5,130.5,129.9,129.6 ,128.5,128.4,127.8,127.7,86.3,73.6,72.7,70.9,69.4,66.0,64.9,58.9,24.1,21.2,21.0,19.8,13.8.

[0149] Experimental Example: Preparation of 40-Tetrabutylammonium Sulfate Derivative

[0150]

[0151] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-40 tetrabutylammonium sulfate (12.0 mg, 38%) was used. 1H NMR (600MHz, Chloroform-d, 298K): δ7.51–7.48(m,2H),7.36–7.20(m,13H),7.05(d,J=9.1Hz,2H),6.7 2(d,J=9.1Hz,2H),5.33(d,J=10.8Hz,1H),4.93(d,J=10.9Hz,1H),4.88(d,J=7.8Hz,1H),4.76(d,J=10. 9Hz,1H),4.71(d,J=10.9Hz,1H),4.63–4.55(m,2H),4.44–4.38(m,2H),3.79–3.75(m,2H),3.74(s,3H), 3.69–3.62(m,1H),3.26–3.16(m,8H),1.60–1.56(m,8H),1.41(h,J=7.4Hz,8H),0.98(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ155.1,151.9,139.8,139.3,138.8,128.8,128.4,128.3,128.3,128.0,127.7,12 7.6,127.3,127.1,118.3,114.6,102.5,83.6,81.7,76.6,75.5,75.3,73.4,70.8,58.9,55.8,29.8,24.1,19.9,13.8.

[0152] Experimental Example 41: Preparation of Sugar Derivative 1-41 Tetrabutylammonium Sulfate

[0153]

[0154] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-41 tetrabutylammonium sulfate (18.0 mg, 53%) was used. 1H NMR (500MHz, Chloroform-d, 298K): δ7.39–7.19(m,15H),4.95(d,J=11.1Hz,1H),4.89–4.83(m,2H),4.7 9–4.74(m,2H),4.63(d,J=12.1Hz,1H),4.57(d,J=3.5Hz,1H),4.38(dd,J=10.8,3.6Hz,1H),4.23(dd,J= 10.8,2.1Hz,1H),3.96(t,J=9.3Hz,1H),3.82–3.76(m,1H),3.70(t,J=8.9Hz,1H),3.51(dd,J=9.7,3.5H z,1H),3.34(s,3H),3.28–3.19(m,8H),1.65–1.55(m,8H),1.41(h,J=7.4Hz,8H),0.97(t,J=7.4Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ139.3,138.7,138.4,128.7,128.5,128.4,128.3,128.2,127.9,127. 8,127.6,127.4,98.1,82.1,79.7,77.7,75.6,75.1,73.4,69.6,65.4,58.8,55.1,54.3,24.0,19.8,13.8.

[0155] Experimental Example: Preparation of Tetrabutylammonium Sulfate Derivative 1-42-Tetrabutylammonium Sulfate

[0156]

[0157] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-42 tetrabutylammonium sulfate (18.0 mg, 56%) was used. 1H NMR (600MHz, Chloroform-d, 298K): δ7.96(d,J=7.2Hz,2H),7.90(d,J=6.9Hz,1H),7.83(d,J=6.9Hz,1H),7.47 (dt,J=16.5,7.5Hz,2H),7.35–7.24(m,7H),6.11(t,J=9.8Hz,1H),5.50(t,J=10.1Hz,1H),5.24(dd,J=10.1,3 .6Hz,1H),5.20(d,J=3.6Hz,1H),4.42(ddd,J=9.8,6.9,2.2Hz,1H),4.27(d,J=11.2Hz,1H),4.17(dd,J=11.2, 7.0Hz,1H),3.48(s,3H),3.31–3.21(m,8H),1.68–1.58(m,8H),1.42(h,J=7.4Hz,8H),0.98(t,J=7.4Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ166.0,165.9,165.5,133.4,133.2,133.0,130.0,130.0,129.8,129 .5,129.3,129.3,128.5,128.4,128.3,96.7,72.4,71.0,69.8,68.3,65.9,58.9,55.7,24.1,19.8,13.8.

[0158] Example 40: Preparation of trisaccharide derivative 1-43 tetrabutylammonium sulfate

[0159]

[0160] The experimental procedure is shown in Example 1. The amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-43 tetrabutylammonium sulfate (20.0 mg, 59%) was used. 1H NMR (500MHz, Chloroform-d, 298K): δ7.95 (ddd, J=12.6, 8.2, 1.4Hz, 4H), 7.59–7.43 (m, 2H), 7.35 (t, J=7.8Hz ,4H),6.88(d,J=9.0Hz,2H),6.74(d,J=9.0Hz,2H),5.66(t,J=9.8Hz,1H),5.55(dd,J=9.9,7.9Hz,1H),5.10( d,J=7.9Hz,1H),4.68(dd,J=12.9,2.5Hz,1H),4.29(t,J=9.6Hz,1H),4.20(d,J=2.0Hz,1H),3.73(s,3H),3.6 8(dt,J=9.6,2.3Hz,1H),3.27–3.17(m,8H),1.64–1.55(m,8H),1.41(h,J=7.3Hz,8H),0.98(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ166.1,165.6,155.7,151.5,136.0,133.3,133.0,130.0,129.9,129.9, 129.6,128.5,128.3,127.3,118.8,114.6,101.4,76.2,74.2,72.3,68.0,65.3,58.9,55.8,24.0,19.8,13.8.

[0161] Example 44: Preparation of tetrabutylammonium 1-44 sugar derivative

[0162]

[0163] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-44 tetrabutylammonium sulfate (17.0 mg, 49%) was used. 1H NMR (600MHz, Chloroform-d, 298K): δ8.03–7.93 (m, 4H), 7.48 (dddt, J = 8.7, 7.7, 2.9, 1.3Hz, 2H), 7.37–7.31(m,4H),5.71(dd,J=10.8,3.4Hz,1H),5.65(dd,J=10.8,3.6Hz,1H),5.14(d,J=3.6Hz,1 H),4.57(d,J=1.1Hz,1H),4.41(t,J=9.7Hz,1H),4.14–4.10(m,1H),4.05(dd,J=10.9,5.1Hz,1H), 3.39(s,3H),3.30–3.19(m,8H),1.64–1.58(m,8H),1.42(h,J=7.4Hz,8H),0.98(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ166.2,166.0,133.2,133.0,130.2,130.0,129.9, 129.8,128.4,128.4,97.8,70.3,69.5,68.3,66.9,64.0,59.0,55.6,24.1,19.8,13.8.

[0164] Experimental Example: Preparation of 1-4,5-Tetrabutylammonium Sulfate, a Sugar Derivative

[0165]

[0166] The experimental procedure is shown in Example 1. The amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-45 tetrabutylammonium sulfate (17.0 mg, 49%) was used. 1 H NMR (600MHz, Chloroform-d, 298K): δ7.33–7.15(m,10H),5.09(d,J=12.2Hz,1H),5.03(d,J=12. 4Hz,1H),4.92(d,J=11.3Hz,2H),4.70–4.64(m,2H),4.58(d,J=12.5Hz,1H),4.09(d,J=12.7Hz,1 H),3.96(t,J=9.5Hz,1H),3.87(t,J=10.6Hz,1H),3.64(d,J=9.7Hz,1H),3.54(t,J=9.7Hz,1H),3 .29(s,3H),3.24–3.16(m,8H),1.66–1.55(m,8H),1.43(q,J=6.9Hz,8H),1.00(t,J=7.0Hz,12H).13 C NMR (150MHz, Chloroform-d, 298K): δ156.3,139.3,136.6,128.6,128.3,128.2,128.2,12 7.9,127.4,99.2,79.4,74.5,71.5,70.7,66.9,66.0,59.1,55.2,54.7,24.1,19.9,13.8.

[0167] Experimental Example: Preparation of 1-46 Tetrabutylammonium Sulfate, a 46-saccharide derivative

[0168]

[0169] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-46 tetrabutylammonium sulfate (26.0 mg, 84%) was used. 1 H NMR (600MHz, Chloroform-d, 298K): δ7.92–7.90(m,2H),7.87–7.84(m,2H),7.51–7.43(m,2H),7.38–7.29(m,6H),7.19 –7.15(m,2H),7.08–7.01(m,5H),5.67(t,J=9.4Hz,1H),5.29(t,J=9.8Hz,1H),4.86(dd,J=12.3,10.2Hz,2H),4.53(d, J=10.5Hz,1H),4.49(dd,J=11.0,3.3Hz,1H),4.42(dd,J=11.0,2.0Hz,1H),4.05(t,J=9.5Hz,1H),3.76(ddd,J=9.7,3. 3,2.1Hz,1H),3.35–3.25(m,8H),2.27(s,3H),1.70–1.61(m,8H),1.46(hd,J=7.5,1.7Hz,8H),1.01(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ165.8,165.5,138.2,137.6,133.3,133.2,132.3,130.0,130.0,129.8,129.6 ,129.5,128.9,128.4,128.4,128.3,127.7,87.1,78.5,76.3,75.1,74.9,71.1,65.3,59.1,24.2,21.2,19.9,13.9.

[0170] Example 47: Preparation of the sugar derivative 1-47 tetrabutylammonium sulfate

[0171]

[0172] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-47 tetrabutylammonium sulfate (14.0 mg, 44%) was used. 1 H NMR (600MHz, Chloroform-d, 298K): δ7.41 (d, J=7.4Hz, 2H), 7.37–7.21 (m, 15H), 7.06 (d, J=7.9Hz, 2H), 5.45(s,1H),4.87(d,J=10.1Hz,1H),4.82(d,J=10.0Hz,1H),4.71(d,J=11.5Hz,1H),4.65(d,J=11.7Hz, 1H),4.58(d,J=11.8Hz,1H),4.11(t,J=9.4Hz,1H),3.96(dd,J=3.1,1.8Hz,1H),3.82(dd,J=9.2,3.0Hz ,1H),3.21–3.13(m,8H),2.25(s,3H),1.59–1.49(m,8H),1.37(h,J=7.3Hz,8H),0.94(t,J=7.3Hz,12H). 13 C NMR (150MHz, Chloroform-d, 298K): δ138.7,138.5,132.6,130.0,128.9,128.5,128.5,128.4,128.3,12 7.8,127.8,127.7,127.6,86.7,80.2,75.3,74.7,72.6,72.5,72.2,65.7,58.9,24.1,21.2,19.8,13.8.

[0173] Experimental Example: Preparation of 1-48 Tetrabutylammonium Sulfate, a 48-saccharide derivative

[0174]

[0175] The experimental procedure is shown in Example 1. The amount of dimethyl sulfate was increased to 2.0 equivalents, the amount of tetrabutylammonium bisulfate was increased to 2.0 equivalents, and the sugar derivative 1-48 tetrabutylammonium sulfate (26.0 mg, 84%) was used. 1H NMR (500MHz, Chloroform-d, 298K): δ7.90 (ddd, J=11.6, 8.4, 1.3Hz, 4H), 7.49 (dtt, J=7.7, 6.4, 1.3Hz, 2H), 7.35 (td, J=7.7, 5.1Hz, 4H), 7 .26–7.21(m,2H),7.07(dd,J=4.8,1.8Hz,3H),6.87(d,J=9.0Hz,2H),6.74(d,J=9.1Hz,2H),5.73(t,J=9.7Hz,1H),5.49(dd,J=10.0,8.0Hz ,1H),5.09(d,J=8.0Hz,1H),4.92(d,J=10.4Hz,1H),4.59(d,J=10.5Hz,1H),4.55(dd,J=11.1,2.7Hz,1H),4.39(dd,J=11.1,2.0Hz,1H),4 .17(t,J=9.5Hz,1H),3.84(d,J=9.6Hz,1H),3.72(s,3H),3.27–3.18(m,8H),1.66–1.57(m,8H),1.46–1.37(m,8H),0.98(t,J=7.3Hz,12H). 13 CNMR (150MHz, Chloroform-d, 298K): δ165.7,165.5,155.7,151.4,137.5,133.3,133.2,129.9,129.6,129.5,128.9,12 8.5,128.4,128.3,127.8,118.6,114.8,101.0,75.2,75.0,74.8,74.5,72.1,65.4,60.5,59.0,55.7,24.0,19.9,13.8.

[0176] Experiment Example 49: Preparation of 1-hydroxycyclohexylphenyl ketone tetrabutylammonium sulfate

[0177]

[0178] 1-Hydroxycyclohexylphenyl ketone (0.2 mmol), sodium pyrosulfate (0.4 mmol), and tetrabutylammonium hydrogen sulfate (0.22 mmol) were added sequentially to a 4 mL reaction flask. After the addition was complete, the 4 mL reaction flask was sealed and evacuated, then purged with argon gas. This process was repeated three times. Finally, 1 mL of acetonitrile was added to the flask, and the mixture was heated to 80°C for 12 hours. After the reaction was complete, potassium carbonate (0.6 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The organic phase was concentrated and subjected to column chromatography. 1-Hydroxycyclohexylphenyl ketone tetrabutylammonium sulfate (89.4 mg, 85%) was separated using a dichloromethane to methanol eluent at a volume ratio of 20:1. 1 H NMR (400MHz, Chloroform-d, 298K, δ): 8.35 (d, J = 7.6Hz, 2H), 7.42-7.33 (m, 3H), 3.10-3.06 (m, 8H), 2.32 (d, J = 13.7Hz, 2H), 1.92 (t, J =12.1Hz,2H),1.74(t,J=12.0Hz,2H),1.52(p,J=8.5,7.8Hz,10H),1.33(h,J=7.3Hz,8H),1.26-1.21(m,2H),0.94(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 201.9, 136.3, 131.4, 130.3, 127.9, 85.9, 58.5, 33.7, 25.7, 24.0, 21.8, 19.7, 13.8.

[0179] Experimental Example 50: Preparation of 1-hydroxybenzotriazole tetrabutylammonium sulfate

[0180]

[0181] The experimental procedure is shown in Example 49, 1-hydroxybenzotriazole tetrabutylammonium sulfate (70.0 mg, 77%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 7.86 (d, J = 8.4Hz, 1H), 7.79 (d, J = 7.9Hz, 1H), 7.40 (t, J = 7.6Hz, 1H), 7.28(t,J=7.6Hz,1H),3.09-3.04(m,8H),1.54-1.46(m,8H),1.28(p,J=7.4Hz,8H),0.88(t,J=7.2Hz,12H). 13C NMR (101MHz, Chloroform-d, 298K, δ): 143.3, 128.9, 127.5, 124.2, 119.2, 111.5, 58.4, 23.8, 19.5, 13.6.

[0182] Experimental Example 51: Preparation of N-hydroxy-7-azabenzotriazole tetrabutylammonium sulfate

[0183]

[0184] The experimental procedure is described in Example 49, 1-hydroxybenzotriazole tetrabutylammonium sulfate (68.6 mg, 75%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 8.67 (d, J = 4.4Hz, 1H), 8.26 (d, J = 8.3Hz, 1H), 7.32 (dd, J = 8. 4,4.4Hz,1H),3.27-3.22(m,8H),1.64-1.56(m,8H),1.34(h,J=7.4Hz,8H),0.89(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 151.0, 140.7, 134.8, 128.5, 120.2, 58.5, 23.9, 19.6, 13.7.

[0185] Experimental Example 52: Preparation of 4-Phenylenol Tetrabutylammonium Sulfate

[0186]

[0187] The experimental procedure is described in Example 49, 4-phenylphenol tetrabutylammonium sulfate (83.5 mg, 85%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.51-7.44(m,5H),7.40-7.35(m,5H),7.29-7.25(m,1H),3. 14-3.09(m,8H),1.55-1.47(m,8H),1.32(h,J=7.4Hz,8H),0.90(t,J=7.3Hz,12H). 13 C NMR (101MHz, Ch loroform-d, 298K, δ): 153.2, 140.8, 136.3, 128.7, 127.5, 126.9, 126.8, 121.3, 23.8, 19.6, 13.6.

[0188] Experimental Example 53: Preparation of 1-Naphthol Tetrabutylammonium Sulfate

[0189]

[0190] The experimental procedure is described in Example 49, 1-Naphthol Tetrabutylammonium Sulfate (81.8 mg, 88%). 1 H NMR (400MHz, Chloroform-d, 298K, δ): 8.39-8.36 (m, 1H), 7.76-7.70 (m, 2H), 7.53 (d, J = 8.2Hz, 1H), 7.4 2-7.35(m,3H),3.04-3.00(m,8H),1.44(p,J=8.1Hz,8H),1.27(h,J=7.4Hz,8H),0.90(t,J=7.2Hz,12H). 13 C NMR (101MHz, Ch loroform-d, 298K, δ): 149.6, 134.6, 128.0, 127.3, 126.0, 125.4, 123.6, 123.3, 116.4, 58.4, 23.9, 19.7, 13.8.

[0191] Experimental Example 54: Preparation of 4-Ethylphenol Tetrabutylammonium Sulfate

[0192]

[0193] The experimental procedure is described in Example 49, 4-ethylphenol tetrabutylammonium sulfate (72.6 mg, 82%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.23(d,J=8.2Hz,2H),7.05(d,J=8.1Hz,2H),3.16-3.12(m,8H),2.55(q,J=7. 6Hz, 2H), 1.53 (p, J = 7.6Hz, 8H), 1.34 (h, J = 7.3Hz, 8H), 1.16 (t, J = 7.6Hz, 3H), 0.93 (t, J = 7.3Hz, 12H). 13 C NMR (101MHz, Ch loroform-d, 298K, δ): 151.5, 139.4, 128.2, 121.1, 58.5, 28.3, 23.9, 19.7, 15.9, 13.8.

[0194] Experimental Example 55: Preparation of 4-tert-butylphenol tetrabutylammonium sulfate

[0195]

[0196] The experimental procedure is described in Example 49, 4-tert-butylphenol tetrabutylammonium sulfate (81.9 mg, 87%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.25(d,J=7.4Hz,4H),3.19-3.14(m,8H),1.55(p,J=7.7Hz,8H),1.35(h,J=7.3Hz,8H),1.25(s,9H),0.93(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 151.2, 146.2, 125.8, 120.6, 58.6, 34.3, 31.6, 23.9, 19.7, 13.8.

[0197] Experimental Example 56: Preparation of 4-trifluoromethylphenol tetrabutylammonium sulfate

[0198]

[0199] The experimental procedure is described in Example 49, 4-trifluoromethylphenol tetrabutylammonium sulfate (88.0 mg, 91%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.52(d,J=8.7Hz,2H),7.47(d,J=8.7Hz,2H),3.21-3. 17(m,8H),1.63-1.56(m,8H),1.39(h,J=7.4Hz,8H),0.97(t,J=7.3Hz,12H). 13 C NMR (101MHz, Chloroform-d, 298K, δ): 156.5, 126.5-126.2 (m), 126.0-125.0 (m), 120.8, 58.8, 24.0, 19.8, 13.7. 19 F NMR (376MHz, Ch loroform-d, 298K, δ): -61.74.

[0200] Experimental Example 57: Preparation of 4-cyanophenol tetrabutylammonium sulfate

[0201]

[0202] The experimental procedure is described in Example 49, 4-cyanophenol tetrabutylammonium sulfate (71.4 mg, 81%). 1H NMR(400MHz,Ch loroform-d,298K,δ):7.56(d,J=8.5Hz,2H),7.45(d,J=8.6Hz,2H),3.22-3.1 8(m,8H),1.60(p,J=8.4Hz,8H),1.40(h,J=7.4Hz,8H),0.97(t,J=7.3Hz,12H). 13 CNMR (101MHz, Ch loroform-d, 298K, δ): 157.5, 133.5, 121.0, 119.4, 106.3, 58.8, 24.0, 19.8, 13.7.

[0203] Experimental Example 58: Preparation of 4-acetylphenol tetrabutylammonium sulfate

[0204]

[0205] The experimental procedure is described in Example 49, 4-acetylphenol tetrabutylammonium sulfate (75.8 mg, 83%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.90(d,J=8.3Hz,2H),7.45(d,J=8.3Hz,2H),3.26-3.22(m ,8H),2.55(s,3H),1.66-1.58(m,8H),1.46-1.37(m,8H),0.99(t,J=7.3Hz,12H). 13 CNMR (101 MHz, Chloroform-d, 298 K, δ): 197.5, 158.0, 132.3, 130.0, 120.1, 58.9, 26.7, 24.1, 19.8, 13.8. Example 59: Preparation of 2-iodophenol tetrabutylammonium sulfate.

[0206]

[0207] The experimental procedure is described in Example 49, 2-iodophenol tetrabutylammonium sulfate (80.9 mg, 75%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.76-7.72(m,2H),7.24(d,J=7.1Hz,1H),6.76(t,J=7.6Hz,1 H),3.23-3.19(m,8H),1.64-1.56(m,8H),1.43-1.34(m,8H),0.96(t,J=7.3Hz,12H). 13CNMR (101 MHz, Chloroform-d, 298 K, δ): 153.6, 139.0, 129.2, 125.0, 121.0, 89.7, 58.8, 24.1, 19.8, 13.8. Example Sixty: Preparation of 2-Phenylenol Tetrabutylammonium Sulfate

[0208]

[0209] The experimental procedure is described in Example 49, 2-phenylphenol tetrabutylammonium sulfate (66.9 mg, 68%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.91(d,J=8.7Hz,1H),7.69(d,J=7.1Hz,2H),7.37-7.29(m,3H),7.26-7.22(m,2H), 7.09(t,J=7.4Hz,1H),3.06-3.02(m,8H),1.49-1.41(m,8H),1.27(h,J=7.3Hz,8H),0.90(t,J=7.3Hz,12H). 13 CNMR (101MHz, Ch loroform-d, 298K, δ): 150.7, 138.8, 133.0, 130.6, 130.0, 128.2, 128.0, 126.7, 123.6, 121.2, 58.5, 23.9, 19.7, 13.7.

[0210] Experimental Example 61: Preparation of Methyl 3-hydroxybenzoate Tetrabutylammonium Sulfate

[0211]

[0212] The experimental procedure is described in Example 49, methyl 3-hydroxybenzoate tetrabutylammonium sulfate (78.6 mg, 83%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.98(s,1H),7.75(d,J=7.7Hz,1H),7.62(d,J=8.5Hz,1H),7.34(t,J=7.9Hz,1H) ,3.86(s,3H),3.23-3.19(m,8H),1.60(p,J=7.6Hz,8H),1.39(h,J=7.4Hz,8H),0.97(t,J=7.3Hz,12H). 13C NMR (101MHz, Ch loroform-d, 298K, δ): 167.0, 153.7, 131.1, 129.1, 126.1, 124.9, 122.3, 58.8, 52.2, 24.0, 19.8, 13.8.

[0213] Experimental Example 62: Preparation of 3-ethyl-4-chlorophenol tetrabutylammonium sulfate

[0214]

[0215] The experimental procedure is described in Example 49, 3-ethyl-4-chlorophenol tetrabutylammonium sulfate (78.3 mg, 82%). 1 H NMR(400MHz,Ch loroform-d,298K,δ):7.23(s,1H),7.18(d,J=2.4Hz,2H),3.22-3.18(m,8H),2.68(q,J=7.5Hz ,2H),1.63-1.55(m,8H),1.39(h,J=7.4Hz,8H),1.19(t,J=7.5Hz,3H),0.97(t,J=7.3Hz,12H). 13 C NMR (101MHz, Ch loroform-d, 298K, δ): 152.4, 142.1, 129.5, 128.4, 122.3, 119.9, 58.8, 27.0, 24.0, 19.8, 14.0, 13.8.

[0216] Many specific details have been set forth in the foregoing description to provide a full understanding of the present invention. However, the above description is merely a preferred embodiment of the present invention, and the present invention can be implemented in many other ways different from those described herein. Therefore, the present invention is not limited to the specific embodiments disclosed above. Furthermore, any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention, or modify them into equivalent experimental examples, using the methods and techniques disclosed above, without departing from the scope of the present invention. Any simple modifications, equivalent changes, and modifications made to the above experimental examples based on the technical essence of the present invention, without departing from the content of the present invention, shall still fall within the scope of protection of the present invention.

Claims

1. A method for preparing an organic sulfate, characterized in that, The organic sulfate has the following general molecular formula: in, R 1 The radicals are hydrocarbon, alkoxy, alkylthio, cyano, trifluoromethyl, aldehyde, and nitro. R 2 The radicals are hydrocarbon, alkoxy, alkylthio, cyano, trifluoromethyl, aldehyde, and nitro. R 3 The radicals are hydrocarbon, alkoxy, alkylthio, cyano, trifluoromethyl, aldehyde, and nitro. M is NBu4; The preparation method includes the following steps: using a dialkyl sulfate or pyrosulfate containing a sulfate functional group as a sulfation reagent, the functional group of the hydroxyl compound is transformed by in-situ activation with protons, thereby preparing the organic sulfate; the hydroxyl compound, the dialkyl sulfate or pyrosulfate, and the organic ammonium salt are mixed in a reaction vessel in proportion, the reaction vessel is evacuated, an organic solvent is added to the reaction flask, the reaction is stirred, after the reaction is completed, a quenching reaction is performed, and then column chromatography is performed to obtain the organic ammonium sulfate; The organic ammonium salt is tetrabutylammonium hydrogen sulfate; The dialkyl sulfate has the following general molecular formula: in, R in 1 The derivatives are methyl, ethyl, propyl, n-butyl, and n-pentyl. The pyrosulfate has the following general molecular formula: Where M is a counter cation, and the counter cation is Na, K, NBu4, NEt4, NHEt3; The hydroxy compound is: , or R in the hydroxy compound 1 The radicals are hydrocarbon, alkoxy, alkylthio, cyano, trifluoromethyl, aldehyde, and nitro. R in the hydroxy compound 2 The radicals are hydrocarbon, alkoxy, alkylthio, cyano, trifluoromethyl, aldehyde, and nitro. R in the hydroxy compound 3 It can be a hydrocarbon group, alkoxy group, alkylthio group, cyano group, trifluoromethyl group, aldehyde group, or nitro group.

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