CN117164505A

CN117164505A - Method for synthesizing organic sulfate from dialkyl sulfate or pyrosulfate

Info

Publication number: CN117164505A
Application number: CN202311012144.4A
Authority: CN
Inventors: 李家昆; 岳帅帅; 徐鹏; 丁国平
Original assignee: Hunan University
Current assignee: Hunan University
Priority date: 2023-08-11
Filing date: 2023-08-11
Publication date: 2023-12-05

Abstract

The invention discloses a preparation method of organic sulfate, which is characterized by comprising the following steps of taking dialkyl sulfate or pyrosulfate containing sulfate functional groups as a sulfating reagent, and realizing the conversion of alcohol hydroxyl compound or phenol compound functional groups through in-situ activation of protons so as to prepare the organic sulfate. According to the invention, dialkyl sulfate is used as a source, the electrophilicity of the dialkyl sulfate is improved through in-situ activation of sulfate radical, so that nucleophilic attack of different hydroxyl compounds is completed, and the organic sulfate can be efficiently synthesized by utilizing the mechanism.

Description

Method for synthesizing organic sulfate by dialkyl sulfate or pyrosulfate

Technical Field

The invention relates to the fields of organic chemistry and sulfation, and discloses a novel application of dialkyl sulfate or pyrosulfate as a sulfation reagent.

Background

Organosulfate compounds are widely found in nature and include nucleosides, polypeptides, proteins, steroids, polysaccharides, and pheromones, which play an important role in biological functions such as signal transduction, hormonal regulation, molecular recognition, and detoxification. Meanwhile, the natural drug molecules are subjected to post-sulfation treatment, so that heparin sulfate and chondroitin sulfate can be obtained after the natural drug molecules are subjected to sulfation, and the intermolecular interaction and the combination of proteins and receptors are enhanced. Of interest is the advent of the first organic sulfate-containing antibiotic, avibactam sodium, which has prompted the step-by-step reporting of other novel beta-lactamase inhibitors. Since organosulfate compounds play an important role in a variety of important biological processes, their synthesis has become a focus of considerable interest.

The most common method of introducing sulfate groups into compounds to date has been the reaction of hydroxyl or amine groups in the compounds with sulfur trioxide (SO ₃ ) The nucleophilic addition reaction of the complex of the organic amine takes place. The method has good universality, but has great limitation that the method completely depends on the nucleophilicity of hydroxyl and amino functional groups in a substrate (Umesh R.Desa i.tetrahedron,2010,66,2907-2918;Al an M.Jones.Chem.Commun, 2019,55,4319-4322), and has high sulfur trioxide toxicity and poor biocompatibility. Other methods, such as esterification of hydroxyl-containing compounds with sulfuric acid, addition of concentrated sulfuric acid to olefins, are theoretically possible; the weak nucleophilicity of sulfate radical makes the sulfate radical have strict requirement on the substrate and strict reaction condition, and the methods have not great application value. Therefore, developing a brand new sulfating reagent and a sulfating method with mild reaction conditions has important significance.

Disclosure of Invention

The invention discloses an organic sulfate and a preparation method thereof, which aim to solve the problems of limited sulfation substrate and high toxicity of sulfation reagent in the prior art.

The preparation method of the organic sulfate comprises the following steps of taking dialkyl sulfate or pyrosulfate containing sulfate functional groups as a sulfating reagent, and realizing the conversion of hydroxyl compounds or phenol compound functional groups through in-situ activation of protons to the dialkyl sulfate or pyrosulfate. The molecular formulas of the dialkyl sulfate and the pyrosulfate are respectively as follows:

wherein R1 comprises a hydrocarbon group which is more than or equal to C1, such as methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl and the like; m is a counter cation including, but not limited to, na, K, NBu ₄ ，NEt ₄ ，NHEt ₃ Etc.

An organic sulfate salt having the following molecular formula:

wherein R comprises a substituted hydrocarbon group and a substituted aromatic (hetero) group, the substituent comprises a hydrocarbon group, an aryl group, an alkoxy group, an alkylthio group, a silicon group, a boron group, an ester group, an amide group, a cyano group, a trifluoromethyl group, an aldehyde group, a nitro group, an alkenyl group, an alkynyl group, an azide group or a halogen atom which are not less than C1, and the number of the substituent is one or more. M is a counter cation including, but not limited to, na, K, NBu ₄ ，NEt ₄ ，NHEt ₃ Etc.

According to the invention, dialkyl sulfate and pyrosulfate are used as sources, are activated in situ by protons and act on different hydroxyl compound substrates, and are used as a sulfate donor to participate in the conversion of organic functional groups, so that the organic sulfate is efficiently synthesized. The dialkyl persulfates used in the present invention are dimethyl sulfate, diethyl sulfate, dipropyl sulfate, diisopropyl sulfate, dibutyl sulfate, etc. and suitable hydroxyl compounds include, but are not limited to, primary alcohols, secondary alcohols, tertiary alcohols, nitrogen-hydroxyl compounds, phenols, saccharides, etc.

Detailed Description

The technical scheme of the invention is specifically described by the following specific embodiments, and the components or devices in the following examples are all general standard components or components known to the skilled person, and the structures and principles of the components or devices are all known to the skilled person through technical manuals or through routine experimental methods unless specifically described.

General description

Abbreviations are used in the examples of implementation,the meaning is as follows: me is methyl, ph is phenyl, bu is butyl, CH ₃ CN is acetonitrile, DMS is dimethyl sulfate, DPS is diisopropyl sulfate, NMR is nuclear magnetic resonance.

The anhydrous and anaerobic experimental conditions according to the invention are all carried out according to the Schlenk (smith) technical standard. The solvents used are purified and dried by standard methods before use, and the compounds used are commercially available or synthesized according to existing literature methods and purified before use.

The mechanism of the conventional sulfation reaction is to carry out addition reaction on an active sulfur trioxide complex (electrophilic) in an alkaline system by utilizing the nucleophilicity of a reaction initiator; or by virtue of the weak nucleophilicity of the sulfate anion. The core of the present invention is dialkyl sulfate, which makes it not just an alkylating agent, but an important sulfate functional agent. The invention is carried out by in-situ activation of dialkyl sulfate (taking dimethyl sulfate as an example) by acid to improve the electrophilicity of the dialkyl sulfate, and the mechanism of the sulfation reaction is shown as follows:

the structure of pyrosulfate is S ₂ O ₇ ^2- Containing structural units SO ₃ The method comprises the steps of carrying out a first treatment on the surface of the The nature of the above dialkyl sulfate as a sulfating agent is to transfer the SO itself ₃ Functional groups to hydroxyl-based substrates. Therefore, in view of the activation model of dialkyl sulfate, the sulfur atom of pyrosulfate is activated under acidic conditions to improve the electrophilicity of the pyrosulfate, and SO can be realized after attack by hydroxyl nucleophile ₃ The introduction of functional groups realizes the sulfation reaction of hydroxyl compounds, and the mechanism general formula is as follows:

example 1

This example focuses on a method for preparing an organosulfate compound using a hydroxyl compound (alkyl alcohol compound) as a substrate and dialkyl sulfate as a sulfate source, which has the general formula:

wherein R comprises a substituted hydrocarbyl group and a substituted aryl (hetero) group. The substituent comprises more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amido, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl, azido or halogen atom, and the number of the substituent is one or more. R1 includes C1 or more hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl and the like.

The ammonium salt is triethylamine, diethylamine, 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, tetraethylammonium p-toluenesulfonate, tetraethylammonium iodide, tetraethylammonium perchlorate, ammonium iodide, di-t-butyltetrabutylammonium phosphate, tetramethylammonium hydrogen sulfate, tetrapropylammonium bromide, or the like.

Example two

This example focuses on the preparation of an organosulfate compound using a phenol compound as a substrate and pyrosulfate as a sulfate source, which has the general formula:

wherein R is ¹ Comprises more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amido, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or halogen atom, and substituent R ¹ The number of (2) is 1-5; m is a counter cation; the base is an organic base or an inorganic base, including LiHCO ₃ 、Li ₂ CO ₃ 、Li ₃ PO ₄ 、LiH ₂ PO ₄ 、Li ₂ HPO ₄ 、LiHC ₂ O ₄ 、Li ₂ C ₂ O ₄ 、CH ₃ COOLi、HCOOLi、LiOH、MeOLi、t-BuOLi、NaHCO ₃ 、Na ₂ CO ₃ 、Na ₃ PO ₄ 、NaH ₂ PO ₄ 、Na ₂ HPO ₄ 、NaHC ₂ O ₄ 、Na ₂ C ₂ O ₄ 、CH ₃ COONa、HCOONa、NaOH、MeONa、t-BuONa、KHCO ₃ 、K ₂ CO ₃ 、K ₃ PO ₄ 、KH ₂ PO ₄ 、K ₂ HPO ₄ 、KHC ₂ O ₄ 、K ₂ C ₂ O ₄ 、CH ₃ COOK、HCOOK、KOH、KOLi、t-BuOK、NH ₄ HCO ₃ 、(NH ₄ ) ₂ CO ₃ 、(NH ₄ ) ₃ PO ₄ 、(NH ₄ )H ₂ PO ₄ 、(NH ₄ ) ₂ HPO ₄ 、NH ₄ HC ₂ O ₄ 、(NH ₄ ) ₂ C ₂ O ₄ Ammonia, triethylamine, diisopropylamine, trimethylamine, piperidine, pyridine, ammonium salts were as in example one.

Example III

This example focuses on a method for preparing an organosulfate compound from N-hydroxy compounds as substrate and pyrosulfate as sulfate source, which has the general formula:

wherein R1 comprises a hydrocarbyl group, an aryl group, an alkoxy group, an alkylthio group, a silicon group, a boron group, an ester group, an amide group, a cyano group, a trifluoromethyl group, an aldehyde group, a nitro group, an alkenyl group, an alkynyl group or a heteroatom which are more than or equal to C1; r2 comprises hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or heteroatom which are more than or equal to C1; m is a counter cation; the base and ammonium salt were the same as in example two.

Experimental example preparation of N- (3-hydroxypropyl) phthalimide tetrabutylammonium sulfate

N- (3-hydroxypropyl) phthalimide (0.2 mmol), dimethyl sulfate (0.24 mmol) and tetrabutylammonium bisulfate (0.24 mmol) are sequentially added into a 4mL reaction bottle, and after the addition, the 4mL reaction bottle is sealed and vacuumized, then argon is filled, and the operation is repeated for 3 times. Finally, 1mL of acetonitrile was added to the flask, and the mixture was allowed to react for 12 hours at 80 degrees celsius under heating. After the reaction was completed, the organic phase was concentrated and subjected to column chromatography, and N- (3-hydroxypropyl) phthalimide tetrabutylammonium sulfate (84.3 mg, 80%) was separated with an eluent having a volume ratio of dichloromethane to methanol 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＝7.5Hz,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.

Experimental example preparation of Di-p-fluorophenylethanol tetrabutylammonium sulfate

Experimental procedure one example one, p-fluorophenylethanol tetrabutylammonium sulfate (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). ¹³ C 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.

Experimental example preparation of tetrabutylammonium Tri3-bromophenyl ethanol sulfate

Experimental procedure is given in example I, tetrabutylammonium 3-bromophenyl ethanol 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.

Experimental example preparation of tetrabutylammonium tetra1-naphthalenol sulfate

Experimental procedure one, example one, gives a quantity of tetrabutylammonium bisulfate raised to 0.4mmol, tetrabutylammonium 1-naphthaleneethoxide (79.9 mg, 81%). ¹ H 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.

Experimental example preparation of tetrabutylammonium Penta4-nitrophenylethanol sulfate

Experimental procedure was followed for example one, tetrabutylammonium 4-nitrophenylethanol 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.

Experimental example preparation of tetrabutylammonium hexa4-cyanophenethyl alcohol sulfate

Experimental procedure is given in example I, tetrabutylammonium 4-cyanophenethyl alcohol sulfate (67.5 mg, 72%). ¹ H 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.

Experimental example preparation of tetrabutylammonium hepta4-tert-butylphenyl ethanol sulfate

Experimental procedure is given in example I, tetrabutylammonium 4-tert-butylphenol sulfate (81.3 mg, 81%). ¹ H NMR(400MHz,Chloroform-d,298K,δ):7.23(d,J＝8.3Hz,2H),7.12(d,J＝8.3Hz,2H),4.14(t,J＝7.8Hz,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.

Experimental example preparation of tetrabutylammonium Octa4-methoxyphenylethanol sulfate

Experimental procedure is given in example I, tetrabutylammonium 4-methoxyphenylethanol sulfate (77.7 mg, 82%). ¹ H NMR(400MHz,Chloroform-d,298K,δ):7.13(d,J＝8.5Hz,2H),6.77(d,J＝7.5Hz,2H),4.15(t,J＝7.6Hz,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.

Experimental example nine preparation of tetrabutylammonium 2, 5-dichlorophenyl ethanol sulfate

Experimental procedure is given in example I, tetrabutylammonium 2, 5-dichlorophenyl ethanol 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.

Experimental example preparation of Ten-Methylphenethyl alcohol tetrabutylammonium sulfate

Experimental flow is seen in example I, with the amount of tetrabutylammonium bisulfate raised to 0.4mmol, and with the amount of mesityl oxide tetrabutylammonium sulfate (87.2 mg, 90%). ¹ H 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.

Experimental example preparation of tetrabutylammonium undecylenate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol and lower tetrabutylammonium allylpentanol sulfate (75.3 mg, 92%). 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.

Experimental example preparation of tetrabutylammonium laurynylpentanol sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol and lower tetrabutylammonium acetylenic pentanol (70.6 mg, 87%). ¹ H NMR(400MHz,Chloroform-d,298K,δ):4.04(t,J＝6.3Hz,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.

Experimental example preparation of tridecyl-3-phenyl-2-propyn-1-ol tetrabutylammonium sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol, and give 3-phenyl-2-propyn-1-ol tetrabutylammonium sulfate (57.2 mg, 63%). 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.

Experimental example preparation of tetrabutylammonium sulfate of fourteen 4-vinylbenzyl alcohol

The experimental flow is shown in the example I, the dimethyl sulfate is changed into diisopropyl sulfate (1.2 equiv),the amount of tetrabutylammonium bisulfate to be raised was 0.4mmol, and 4-vinylbenzyl alcohol tetrabutylammonium sulfate (50.3 mg, 55%). ¹ H 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.

Experimental example preparation of pentadecyl 4-boronic acid pinacol ester benzyl alcohol tetrabutyl ammonium sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol, and 4-boronic acid pinacol ester benzyl alcohol tetrabutylammonium sulfate (88.1 mg, 79%). 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 C NMR(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.

Experimental example preparation of tetrabutylammonium cetylbenzyl alcohol 4-formylbenzyl sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv.) and raise the amount of tetrabutylammonium bisulfate to 0.4mmol, 4-formylbenzyl alcohol tetrabutylammonium sulfate (64.1 mg, 70%). ¹ H 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.

Experimental example preparation of heptadeca4-methylsulfonyl benzyl alcohol tetrabutylammonium sulfate

Experimental procedure one, example one, changes dimethyl sulfate to diisopropyl sulfate (1.2 equiv.) and increases tetrabutylammonium bisulfate usage to 0.4mmol, 4-methylsulfonyl benzyl alcohol tetrabutylammonium sulfate (73.2 mg, 72%). 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.

Experimental example preparation of octadecyl thiophene 3-ethanol tetrabutylammonium sulfate

Experimental procedure one example one, thiophene 3-ethanol tetrabutylammonium sulfate (71.8 mg, 80%). ¹ H 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.

Experimental example preparation of tetrabutylammonium sulfate of nineteen trichloroethanol

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol and add tetrabutylammonium trichloroethanol sulfate (31.9 mg, 34%). 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.

Experimental example preparation of tetrabutylammonium 4-phenyl-2-butoxide

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv.) and raise the amount of tetrabutylammonium bisulfate to 0.4mmol, 4-phenyl-2-butanol tetrabutylammonium sulfate (79.3 mg, 84%). ¹ H 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.

Experimental example preparation of methyl-tetra-butyl ammonium-icosa3-hydroxycaproate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv.) and raise tetrabutylammonium bisulfate to 0.4mmol and tetrabutylammonium methyl 3-hydroxycaproate (38.2 mg, 41%). 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.

Experimental example preparation of tetrabutylammonium Sedocodi 2-indenol sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv.) and raise the amount of tetrabutylammonium bisulfate to 0.4mmol and tetrabutylammonium 2-indenol sulfate (66.5 mg, 73%). 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),3.25-3.23(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.

Experimental example preparation of tetra-butyl ammonium docusate of tricosal-menthol

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol and give DL-menthol tetrabutylammonium sulfate (68.8 mg, 72%). 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.

Experimental example preparation of tetracosanol-tetrabutylammonium sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv.) and raise the amount of tetrabutylammonium bisulfate to 0.4mmol and tetrabutylammonium 2-adamantanol sulfate (88.9 mg, 94%). 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 C NMR(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.

Experimental example preparation of tetracyclododecanol tetrabutylammonium sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol and add tetrabutylammonium cyclododecanol sulfate (84.8 mg, 84%). 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.

Experimental example preparation of tetrabutylammonium hexacosyl-4-piperidinol sulfate

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol, N-Tosyl-4-piperidinol tetrabutylammonium sulfate (92.2 mg, 80%). 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 Preparation of Twenty-seven DL-pantolactone tetrabutylammonium sulfate by C NMR (101 MHz, chloroform-d,298K, delta): 143.6,133.2,129.7,127.6,70.6,58.7,43.2,31.0,23.9,21.6,19.7,13.7

Experimental procedure one example one, changes dimethyl sulfate to diisopropyl sulfate (1.2equiv), the amount of tetrabutylammonium bisulfate raised was 0.4mmol, and DL-pantolactone tetrabutylammonium sulfate (29.8 mg, 33%). 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.

Experimental example preparation of Eeight 4-chloro-6, 7-dihydro-5H-cyclopenta [ B ] pyridin-7-ol tetrabutylammonium sulfate

Experimental procedure As shown in example I, changing dimethyl sulfate to diisopropyl sulfate (1.2 equiv), increasing the amount of tetrabutylammonium bisulfate to 0.4mmol, 4-chloro-6, 7-dihydro-5H-cyclopenta [ B ]]Tetrabutylammonium pyridin-7-ol sulfate (39.2 mg, 40%). 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.

Experimental example twenty-nine angstrom karritten tetrabutylammonium sulfate preparation

Experimental procedure is given in example one, ekaritine 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.

Experimental example preparation of Butylammonium sulfate of Aloe thirty-Dacron Huang Susi

Experimental procedure one, example one, changes dimethyl sulfate to diisopropyl sulfate (1.2 equiv), and increases tetrabutylammonium bisulfate usage to 0.4mmol, aloe vera, huang Susi butylammonium sulfate (73.4 mg, 62%). 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),7.22(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):192.6,181.6,162.8,162.5,149.3,137.1,133.6,133.3,124.6,122.4,119.9,118.6,115.8,114.7,67.4,58.7,23.9,19.7,13.7.

Experimental example preparation of tertrabutyl ammonium sulfate of thirty-one ospemide

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol, and give ospemium tetrabutylammonium sulfate (111.9 mg, 80%). ¹ H 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.

Experimental example preparation of tetrabutylammonium tetradifererate of tetradiferesterone

Experimental procedure one, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), raise tetrabutylammonium bisulfate to 0.4mmol, and tetrabutylammonium testosterone sulfate (107.1 mg, 88%). 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). ¹³ C 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.

Experimental example preparation of Dioscorea thirty-three saponin tetrabutylammonium sulfate

Experimental procedure one example I, 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),1.51-1.35(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.

Experimental example preparation of tetrathirty-cholesterol tetrabutylammonium sulfate

Experimental procedure in example I, change dimethyl sulfate to diisopropyl sulfate (1.2 equiv), promoteTetrabutylammonium bisulfate was used in an amount of 0.4mmol, and cholesterol tetrabutylammonium sulfate (69.3 mg, 49%). 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),2.00-1.88(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):141.0,121.7,58.8,56.8,56.2,50.2,42.4,39.9,39.6,37.4,36.6,36.3,35.9,32.0,31.97,29.2,28.3,28.1,24.4,24.1,23.9,22.9,22.7,21.1,19.8,19.5,18.8,13.8,12.0.

Experimental example preparation of thirty-five sugar derivative 1-35 tetrabutylammonium sulfate

Experimental procedure is given in example one, sugar derivative 1-35 tetrabutylammonium sulfate (12.0 mg, 38%). ¹ H 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.

Experimental example preparation of thirty-six sugar derivative 1-36 tetrabutylammonium sulfate

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative is 1-36 tetrabutylammonium sulfate (26.0 mg, 81%). ¹ H 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＝9.5Hz,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):δ139.4,138.7,138.4,137.4,128.8,128.5,128.4,128.3,128.3,128.0,127.8,127.7,127.6,127.4,95.4,82.1,79.8,77.8,75.5,75.1,73.1,70.0,68.8,65.4,58.8,24.0,19.8,13.8.

Experimental example preparation of thirty-seven sugar derivative 1-37 tetrabutylammonium sulfate

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative is 1-37 tetrabutylammonium sulfate (26.0 mg, 81%). ¹ H 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＝9.5,3.9,2.1Hz,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):δ138.8,138.3,138.2,137.5,131.7,130.5,129.9,128.8,128.5,128.4,128.3,127.9,127.8,127.7,127.6,88.0,86.7,80.8,78.2,77.6,75.7,75.4,75.2,65.4,58.9,24.1,21.2,19.8,13.8,13.8.

Experimental example preparation of thirty-eight sugar derivative 1-38 tetrabutylammonium sulfate

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative is 1-38 tetrabutylammonium sulfate (18.0 mg, 56%). ¹ H 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(dq,J＝14.2,6.9Hz,8H),0.94(t,J＝7.3Hz,12H). ¹³ C NMR(150MHz,Chloroform-d,298K):δ169.6,166.0,138.2,137.4,132.9,132.2,132.0,130.8,130.1,129.7,128.3,127.7,127.5,86.2,74.0,72.7,71.2,69.8,68.9,58.9,54.4,52.1,24.1,21.2,19.8,13.8.

Experimental example preparation of thirty-nine sugar derivative 1-39 tetrabutylammonium sulfate

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative is 1-39 tetrabutylammonium sulfate (22.0 mg, 69%). ¹ H 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.

Experimental example preparation of forty sugar derivative 1-40 tetrabutylammonium sulfate

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative is 1-40 tetrabutylammonium sulfate (12.0 mg, 38%). ¹ H NMR(600MHz,Chloroform-d,298K):δ7.51–7.48(m,2H),7.36–7.20(m,13H),7.05(d,J＝9.1Hz,2H),6.72(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):δ155.1,151.9,139.8,139.3,138.8,128.8,128.4,128.3,128.3,128.0,127.7,127.6,127.3,127.1,118.3,114.6,102.5,83.6,81.7,76.6,75.5,75.3,73.4,70.8,58.9,55.8,29.8,24.1,19.9,13.8.

Experimental example preparation of forty-first sugar derivative 1-41 tetrabutylammonium sulfate

Experimental procedure one, example one, gives 2.0 equivalents of dimethyl sulfate and 2.0 equivalents of tetrabutylammonium bisulfate, sugar derivatives 1-41 tetrabutylammonium sulfate (18.0 mg, 53%). ¹ H NMR(500MHz,Chloroform-d,298K):δ7.39–7.19(m,15H),4.95(d,J＝11.1Hz,1H),4.89–4.83(m,2H),4.79–4.74(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＝9.7,3.5Hz,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.

Experimental example preparation of Tetradecadisaccharide derivative 1-42 tetrabutylammonium sulfate

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative is 1-42 tetrabutylammonium sulfate (18.0 mg, 56%). ¹ H 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.

Experimental example preparation of Tetradecyltriase derivative 1-43 tetrabutylammonium sulfate

Experimental procedure one, example one, gives a 2.0 equivalent amount of tetrabutylammonium bisulfate to give 1-43 tetrabutylammonium bisulfate as sugar derivative (20.0 mg, 59%). ¹ H 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),3.68(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.

Experimental example preparation of forty-four sugar derivative 1-44 tetrabutylammonium sulfate

Experimental procedure one, example one, gives 2.0 equivalents of dimethyl sulfate and 2.0 equivalents of tetrabutylammonium bisulfate, sugar derivatives 1-44 tetrabutylammonium sulfate (17.0 mg, 49%). ¹ H 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,1H),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.

Experimental example preparation of forty-five sugar derivative 1-45 tetrabutylammonium sulfate

Experimental procedure one, example one, gives a 2.0 equivalent amount of tetrabutylammonium bisulfate to give 1-45 tetrabutylammonium bisulfate as sugar derivative (17.0 mg, 49%). 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,1H),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):δ156.3,139.3,136.6,128.6,128.3,128.2,128.2,127.9,127.4,99.2,79.4,74.5,71.5,70.7,66.9,66.0,59.1,55.2,54.7,24.1,19.9,13.8.

Experimental example preparation of the forty-hexasaccharide derivative 1-46 tetrabutylammonium sulfate

Experimental procedure one, example one, 2.0 equivalents of dimethyl sulfate was used, 2.0 equivalents of tetrabutylammonium bisulfate was used, and 1-46 tetrabutylammonium sulfate (26.0 mg, 84%) of the sugar derivative 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.

Experimental example forty-seven sugar derivative 1-47 tetrabutylammonium sulfate preparation

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative 1-47 tetrabutylammonium sulfate (14.0 mg, 44%). 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):δ138.7,138.5,132.6,130.0,128.9,128.5,128.5,128.4,128.3,127.8,127.8,127.7,127.6,86.7,80.2,75.3,74.7,72.6,72.5,72.2,65.7,58.9,24.1,21.2,19.8,13.8.

Experimental example forty-eight sugar derivative 1-48 preparation of tetrabutylammonium sulfate

Experimental procedure one, example one, the amount of dimethyl sulfate is 2.0 equivalents, the amount of tetrabutylammonium bisulfate is 2.0 equivalents, and the sugar derivative is 1-48 tetrabutylammonium sulfate (26.0 mg, 84%). ¹ H 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 C NMR(150MHz,Chloroform-d,298K):δ165.7,165.5,155.7,151.4,137.5,133.3,133.2,129.9,129.6,129.5,128.9,128.5,128.4,128.3,127.8,118.6,114.8,101.0,75.2,75.0,74.8,74.5,72.1,65.4,60.5,59.0,55.7,24.0,19.9,13.8.

Experimental example forty-nine preparation of tetrabutylammonium hydroxycyclohexyl phenyl ketone sulfate

To a 4mL reaction flask, 1-hydroxycyclohexyl phenyl ketone (0.2 mmol), sodium pyrosulfate (0.4 mmol), tetrabutylammonium bisulfate (0.22 mmol) were sequentially added, and after the addition, the 4mL reaction flask was sealed and evacuated, and then argon was introduced, and the operation was repeated 3 times. Finally, 1mL of acetonitrile was added to the flask, and the mixture was allowed to react for 12 hours at 80 degrees celsius under heating. After the reaction was completed, potassium carbonate (0.6 mmol) was added thereto and stirred at room temperature for 1 hour. The organic phase was concentrated and then subjected to column chromatography, and 1-hydroxycyclohexyl phenyl ketone tetrabutylammonium sulfate (89.4 mg, 85%) was separated using an eluent having a volume ratio of dichloromethane to methanol 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.

Experimental example fifty 1-hydroxybenzotriazole tetrabutylammonium sulfate preparation

The experimental procedure is given in the example forty-nine, 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). ¹³ C 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.

Experimental example preparation of fifty-one-hydroxy-7-aza-benzotriazol tetrabutylammonium sulfate

The experimental procedure is given in the example forty-nine, 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.

Experimental example preparation of fifty-two 4-phenylphenol tetrabutylammonium sulfate

The experimental procedure is given in the example forty-nine, 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.

Experimental example fifty-three 1-naphthol tetrabutylammonium sulfate preparation

The experimental procedure is given in the example forty-nine, 1-naphthol tetrabutylammonium sulfate (81.8 mg, 88%). ¹ H NMR(400MHz,Ch loroform-d,298K,δ):8.39-8.36(m,1H),7.76-7.70(m,2H),7.53(d,J＝8.2Hz,1H),7.42-7.35(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.

Experimental example fifty-four 4-ethylphenol tetrabutyl ammonium sulfate preparation

The experimental procedure is found in the example forty-nine, 4-ethylphenol tetrabutyl ammonium 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.

Experimental example fifty-five preparation of 4-tert-butylphenol tetrabutylammonium sulfate

The experimental procedure is given in the example forty-nine, 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.

Experimental example fifty-six 4-trifluoromethyl phenol tetrabutylammonium sulfate preparation

The experimental procedure is given in the example forty-nine, 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.

Experimental example fifty-seven preparation of tetrabutylammonium 4-cyanophenol sulfate

The experimental procedure was found to be that of example forty-nine, 4-cyanophenol tetrabutylammonium sulfate (71.4 mg, 81%). ¹ H NMR(400MHz,Ch loroform-d,298K,δ):7.56(d,J＝8.5Hz,2H),7.45(d,J＝8.6Hz,2H),3.22-3.18(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.

Experimental example fifty-eight preparation of 4-acetylphenol tetrabutylammonium sulfate

The experimental procedure is given in the example forty-nine, 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 Preparation of C NMR (101MHz,Ch loroform-d,298K, delta): 197.5,158.0,132.3,130.0,120.1,58.9,26.7,24.1,19.8,13.8 Experimental example fifty-nine 2-iodophenol tetrabutylammonium sulfate

The experimental procedure was found to be that of the example forty-nine, 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,1H),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). ¹³ Preparation of sexagesimal 2-phenylphenol tetrabutylammonium sulfate by C NMR (101MHz,Ch loroform-d,298K, delta): 153.6,139.0,129.2,125.0,121.0,89.7,58.8,24.1,19.8,13.8

The experimental procedure is given in the example forty-nine, 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.

Experimental example preparation of methyl-hexadeca-3-hydroxybenzoate tetrabutylammonium sulfate

Experimental flowSee example forty-nine, 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). ¹³ C 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.

Experimental example preparation of sexagesimal 3-ethyl-4-chlorophenol tetrabutylammonium sulfate

The experimental procedure is given in the example forty-nine, 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.

In the above description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, the foregoing description is only a preferred embodiment of the invention, which can be practiced otherwise than as specifically described herein, and therefore the invention is not limited to the specific details disclosed herein. And any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modify equivalent experimental examples of equivalent variations by using the methods and technical contents disclosed above without departing from the scope of the technical solution of the present invention. Any simple modification, equivalent variation and modification of the above experimental examples according to the technical substance of the present invention without departing from the technical proposal of the present invention still falls within the scope of the technical proposal of the present invention.

Claims

1. A preparation method of organic sulfate is characterized by comprising the following steps of taking dialkyl sulfate or pyrosulfate containing sulfate functional groups as a sulfating reagent, and realizing the conversion of hydroxyl compound or phenol compound functional groups through in-situ activation of protons so as to prepare the organic sulfate.

2. The method of claim 1, wherein the dialkyl sulfate has the following molecular formula:

wherein R is ¹ Comprises alkyl groups which are more than or equal to C1, wherein the alkyl groups comprise methyl, ethyl, propyl, isopropyl, n-butyl and n-pentyl.

3. The method of claim 1, wherein the pyrosulfate has the following molecular formula:

wherein M is a counter cation comprising Na, K, NBu ₄ ，NEt ₄ ，NHEt ₃ 。

4. The production method according to claim 2, wherein the hydroxyl compound comprises:

wherein R is ¹ Comprises substituted hydrocarbyl and substituted aryl (hetero) groups, wherein the substituted groups comprise more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or halogen atoms, and the number of the substituted groups is one or more.

5. The production method according to claim 2, wherein the hydroxyl compound comprises:

wherein R is ¹ Comprises more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or halogen atoms; r is R ² Comprises alkyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl and alkynyl which are more than or equal to C1.

6. The production method according to claim 2, wherein the hydroxyl compound comprises:

wherein R is ¹ Comprises more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or halogen atoms; r is R ² Comprises alkyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl and alkynyl which are more than or equal to C1; r is R ³ Comprises alkyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl and alkynyl which are more than or equal to C1.

7. A method of preparation according to claim 3, wherein the hydroxy compound comprises an N-hydroxy compound:

wherein R is ¹ Comprises more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or heteroatom; r is R ² Comprises more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amide base, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or heteroatom.

8. A method of preparing as claimed in claim 3, wherein the phenol compound comprises:

wherein R is ¹ Comprises more than or equal to C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon base, boron base, ester base, amido, cyano, trifluoromethyl, aldehyde base, nitro, alkenyl, alkynyl or halogen atom, and substituent R ¹ The number of (2) is 1-5; x is C, N, O, S.

9. The preparation method according to any one of claims 1 to 8, comprising the steps of: mixing the hydroxyl compound or the phenol compound, the dialkyl sulfate or the pyrosulfate and the organic ammonium salt in a reaction container in proportion, vacuumizing the reaction container, adding an organic solvent into the reaction container, stirring for reaction, quenching after the reaction is finished, performing column chromatography to obtain the organic ammonium sulfate salt, and performing ion exchange on the obtained organic ammonium sulfate salt to obtain the organic sodium sulfate salt.

10. An organic sulfate prepared according to the preparation method of any one of claims 1 to 8, wherein the organic sulfate has the following molecular formula:

wherein R comprises a substituted hydrocarbyl group and a substituted aryl (hetero) group, the substituents comprise ≡C1 hydrocarbyl, aryl, alkoxy, alkylthio, silicon, boron, ester, amide, cyano, trifluoromethyl, aldehyde, nitro, alkenyl, alkynyl, azide or halogen atoms, the number of substituents is one or more, M is a counter cation comprising Na, K, NBu ₄ ，NEt ₄ ，NHEt ₃ Etc.