CN117185965A - Preparation method of sulfonic acrylic acid salt compound surfactant - Google Patents
Preparation method of sulfonic acrylic acid salt compound surfactant Download PDFInfo
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- CN117185965A CN117185965A CN202311200082.XA CN202311200082A CN117185965A CN 117185965 A CN117185965 A CN 117185965A CN 202311200082 A CN202311200082 A CN 202311200082A CN 117185965 A CN117185965 A CN 117185965A
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- Prior art keywords
- trifluoromethylsulfonyl
- imide
- bis
- allyl alcohol
- aryl
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- -1 acrylic acid salt compound Chemical class 0.000 title claims abstract description 64
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 24
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 8
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 8
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 7
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 12
- 229940041616 menthol Drugs 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- WFABOCFDABTAPE-UHFFFAOYSA-N calcium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ca+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F WFABOCFDABTAPE-UHFFFAOYSA-N 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 150000001840 cholesterol esters Chemical class 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- MSFHCZUIBARZOS-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide copper(1+) Chemical compound [Cu+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F MSFHCZUIBARZOS-UHFFFAOYSA-N 0.000 claims description 3
- DMFBPGIDUUNBRU-UHFFFAOYSA-N magnesium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Mg+2].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F DMFBPGIDUUNBRU-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 abstract description 3
- 150000007942 carboxylates Chemical class 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 239000000575 pesticide Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- UHBLENXLIAOSGX-HCUGZAAXSA-M sodium;(z)-2-methoxycarbonyl-3-phenylprop-2-ene-1-sulfonate Chemical compound [Na+].COC(=O)C(\CS([O-])(=O)=O)=C\C1=CC=CC=C1 UHBLENXLIAOSGX-HCUGZAAXSA-M 0.000 description 6
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000012000 cholesterol Nutrition 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GOUHYARYYWKXHS-UHFFFAOYSA-N para-formylbenzoic acid Natural products OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-M 4-formylbenzoate Chemical compound [O-]C(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VZGOKIHNKHAORQ-UHFFFAOYSA-N methyl 2-[hydroxy(phenyl)methyl]prop-2-enoate Chemical compound COC(=O)C(=C)C(O)C1=CC=CC=C1 VZGOKIHNKHAORQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005712 Baylis-Hillman reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- YMHOPFPBSLGXDP-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenehexanoate Chemical compound CCCC(O)C(=C)C(=O)OC YMHOPFPBSLGXDP-UHFFFAOYSA-N 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a sulfonic acid group acrylic acid salt compound surfactant. According to the invention, an allyl alcohol compound is directly used as a raw material, sodium sulfite or sodium bisulphite is selected as a sulfonation reagent, bis (trifluoromethylsulfonyl) imide calcium and the like are used as catalysts, potassium hexafluorophosphate is used as a ligand, under the condition, the bis (trifluoromethylsulfonyl) imide calcium and the potassium hexafluorophosphate lead hydroxyl in the allyl alcohol to leave in the form of hydroxyl, and ester groups in the allyl alcohol can be further hydrolyzed into carboxylate, so that the product is generated in an environment-friendly mode under mild conditions. The method has the characteristics of wide substrate range, simple steps, convenient operation, environmental protection, excellent stereoselectivity and broad-spectrum functional group tolerance.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a preparation method of a sulfonic acid group acrylic acid salt compound surfactant.
Background
The surfactant is a compound with surface activity and is an indispensable component in the processing of pesticide preparations. The pesticide composition can make the effective components of the pesticide exert the maximum efficacy in pest control, improve the use efficiency of the pesticide, reduce the use amount of the pesticide and lighten the influence of the pesticide on the environment. In actual processing of pesticide preparations, an ideal effect is hardly achieved by using one surfactant alone, and a surfactant compound system is often adopted. The compound surfactant has synergistic effect, so that the defect of each single surfactant in performance can be overcome, the surface performance is enhanced, the dosage of the surfactant is reduced, the cost is reduced, and the efficiency is improved. Gemini surfactants chemically bond two surfactants having the same hydrophilic head group and hydrophobic carbon chain at or near the head group together by a linking group. Because of its special structure, gemini surfactants have excellent physicochemical properties, and have become a research hotspot in the fields of colloid and interfacial chemistry. The hydrophobic chain of the gemini surfactant can inhibit the gemini surfactant from dissolving in water, the chemical bond action of the coupling group can overcome the hydration of the traditional surfactant and the separation tendency of the hydrophobic chain caused by charge repulsive force between hydrophilic head groups, and the equilibrium distance between the hydrophilic head groups is shortened, so that the surfactant is tightly arranged on a gas/liquid or liquid/liquid two-phase interface, the adsorption of molecules on a surface layer is promoted, and the surface tension or oil-water interfacial tension is reduced.
At present, most of the compound surfactants are synthesized in more than two steps, and intermediate products are also required to be separated and purified, so that the steps are complicated, the cost is high, and the industrial development is not facilitated.
Disclosure of Invention
The invention aims to provide a preparation method of a sulfonic acid group acrylic acid salt compound surfactant.
The invention is realized in such a way that the preparation method of the sulfonic acrylic acid salt compound surfactant comprises the following steps:
(1) Sequentially adding an allyl alcohol compound, a sulfonation reagent, a catalyst and a ligand into a reaction solvent, and stirring and reacting for 17-19 h under the heating condition of 80+/-2 ℃ in an inert gas atmosphere to obtain a reaction solution; wherein the chemical structural formula of the allyl alcohol compound is shown as the following formula:
wherein R is selected from any one of normal aryl, condensed aryl, heteroaryl, cycloalkyl and linear alkyl; the substituent of the n-aryl benzene ring is selected from any one of methoxy, cyano, nitro, tertiary butyl, fluoro, bromo, chloro, ferrocenyl, trimethylsilane ethynyl, menthol ester and cholesterol ester;
the sulfonation reagent is sodium sulfite or sodium bisulfite;
the ligand is potassium hexafluorophosphate;
(2) Removing the reaction solvent in the reaction liquid, and leaching the obtained solid by using dichloromethane to obtain the sulfonic acrylic acid salt compound surfactant with the chemical structural formula shown in the formula (I):
in the formula (I), R is selected from any one of normal aryl, condensed aryl, heteroaryl, cycloalkyl and linear alkyl; the substituent of the n-aryl benzene ring is selected from any one of methoxy, cyano, nitro, tertiary butyl, fluoro, bromo, chloro, ferrocenyl, trimethylsilane ethynyl, menthol ester and cholesterol ester;
x is selected from one of Me group and Na group.
Preferably, in the step (1), the molar volume ratio of the allyl alcohol compound, the sulfonating agent, the catalyst, the ligand and the reaction solvent is 0.4 to 0.8mmol:0.4 to 0.8mmol: 0.004-0.008 mmol: 0.004-0.008 mmol: 3-6 mL.
Preferably, in step (1), the catalyst is selected from any one of calcium bis (trifluoromethylsulfonyl) imide, barium bis (trifluoromethylsulfonyl) imide, magnesium bis (trifluoromethylsulfonyl) imide, and copper bis (trifluoromethylsulfonyl) imide.
Preferably, the catalyst is calcium bis (trifluoromethylsulfonyl) imide.
Preferably, in the step (1), the reaction solvent is formed by mixing an organic solvent and water according to a volume ratio of 1:2; wherein the organic solvent is selected from any one of ethanol, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene, methylene dichloride, acetonitrile, 1, 2-dichloroethane, tetrahydrofuran, 1,4 dioxane and isopropanol.
Preferably, in step (1), the inert gas is argon.
The invention overcomes the defects of the prior art and provides a preparation method of a sulfonic acid group acrylic acid salt compound surfactant. According to the invention, an allyl alcohol compound is directly used as a raw material, sodium sulfite or sodium bisulphite is selected as a sulfonation reagent, bis (trifluoromethylsulfonyl) imide calcium and the like are used as catalysts, potassium hexafluorophosphate is used as a ligand, under the condition, the bis (trifluoromethylsulfonyl) imide calcium and the potassium hexafluorophosphate lead hydroxyl in the allyl alcohol to leave in the form of hydroxyl, and ester groups in the allyl alcohol can be further hydrolyzed into carboxylate, so that the product is generated in an environment-friendly mode under mild conditions.
Wherein, when the sulfonation reagent is sodium sulfite, the reaction process is as follows:
when the sulfonation reagent is sodium bisulphite, the reaction process is as follows:
in the invention, the R group in the allyl alcohol compound is selected from any one of normal aryl, condensed aryl, heteroaryl, cycloalkyl and linear alkyl; the substituent of the n-aryl benzene ring is selected from any one of methoxy, cyano, nitro, tertiary butyl, fluoro, bromo, chloro, ferrocenyl, trimethylsilane ethynyl, menthol ester and cholesterol ester; the heteroaryl group is, for example, furyl or thienyl, and the cycloalkyl group is cyclohexyl. Specifically, the allyl alcohol compound is selected from any of methyl 2-hydroxy (phenyl) methacrylate, methyl 2-hydroxy (4-fluorobenzene) methacrylate, methyl 2-hydroxy (4-trifluoromethylphenyl) methacrylate, methyl 2-hydroxy (4-nitrobenzene) methacrylate, methyl 2-hydroxy (4-oxycarbonyl) methacrylate, methyl 2-hydroxy (4-methoxybenzene) methacrylate, methyl 2-hydroxy (4-tert-butylbenzene) methacrylate, methyl 2-hydroxy (3-fluorobenzene) methacrylate, methyl 2-hydroxy (2-chlorobenzoic acid) methyl 2-hydroxy (3, 5-dimethylbenzene) methacrylate, methyl 2-hydroxy (naphthalen-1-yl) methacrylate, methyl 2-hydroxy (pyridin-3-yl) methacrylate, methyl 2-hydroxy (thiophen-2-yl) methacrylate, ethyl 2-hydroxy (phenyl) methacrylate, tert-butyl 2-hydroxy (phenyl) methacrylate, 4- (2-hydroxy-oxycarbonyl) methyl 2- (2-hydroxy-allyl) benzoate, and menthyl (2-hydroxy) benzoate, 3-hydroxy) methyl (2-hydroxy-phenyl) carboxylate).
The invention realizes the one-pot synthesis of the sulfonic acrylic acid salt compound surfactant without further separation and purification, and the active olefin part carried in the molecule provides space for further development.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
(1) The allyl alcohol used in the preparation method is MoritA-Baylis-Hillman alcohol allyl alcohol raw material with simple synthesis and high conversion rate, and has the characteristics of wide applicable substrate range, such as various substituted phenyl groups and alkyl groups on the allyl alcohol, and low preparation cost; in addition, the preparation method has the characteristics of simple steps, convenient operation, environmental protection, excellent stereoselectivity and broad-spectrum functional group tolerance;
(2) The sulfonic acid group acrylate compound surfactant is a general precursor for preparing related sulfonic acid molecules, has potential pharmaceutical activity and biological activity, and can provide a new way for the synthesis and application of novel compound surfactants.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the compound (Z) -3-phenyl-2- (sulfomethyl) acrylic acid sodium salt in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the compound (Z) -3-phenyl-2- (sulfomethyl) acrylic acid sodium salt in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the compound (Z) -2- (methoxycarbonyl) -3-phenylprop-2-en-1-sulfonic acid sodium salt in example 2 of the present invention;
FIG. 4 is a nuclear magnetic resonance carbon spectrum of the compound (Z) -2- (methoxycarbonyl) -3-phenylprop-2-ene-1-sulfonic acid sodium salt of example 2 of the present invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the compound (Z) -2- (methoxycarbonyl) hex-2-ene-1-sulfonic acid sodium salt of example 3 of the present invention;
FIG. 6 is a nuclear magnetic resonance carbon spectrum of the compound (Z) -2- (methoxycarbonyl) hex-2-ene-1-sulfonic acid sodium salt of example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) In a 10mL Schlenk tube, 0.4mmol of methyl 2- (hydroxy (phenyl) methyl) acrylate, 0.4mmol of sodium sulfite, 0.004mmol of calcium bis (trifluoromethylsulfonyl) imide, 0.004mmol of potassium hexafluorophosphate, 1mL of ethanol and 2mL of water were added successively, and the mixture was stirred under argon at 80℃for 18 hours, wherein the reaction equation was:
(2) After completion of the reaction by TLC, the solvent was removed by a vacuum rotary evaporator and the solid was washed with dichloromethane to give the objective product as pale yellow solid sodium (Z) -3-phenyl-2- (sulfomethyl) acrylate (compound 1) in 93% yield.
Characterization of the compound sodium (Z) -3-phenyl-2- (sulfomethyl) acrylate, the results are shown in FIGS. 1-2, and FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of sodium (Z) -3-phenyl-2- (sulfomethyl) acrylate; FIG. 2 is a nuclear magnetic resonance carbon spectrum of sodium (Z) -3-phenyl-2- (sulfomethyl) acrylate.
Example 2
(1) In a 10mL Schlenk tube, 0.8mmol of methyl 2- (hydroxy (phenyl) methyl) acrylate, 0.8mmol of sodium bisulfite, 0.008mmol of magnesium bis (trifluoromethylsulfonyl) imide, 0.004mmol of potassium hexafluorophosphate, 2mL of dichloromethane and 4mL of water were added sequentially, and stirred under argon at 80.+ -. 2 ℃ for 19h, the reaction equation being:
(2) After completion of the reaction by TLC, the solvent was removed by vacuum rotary evaporator and the solid was washed with dichloromethane to give the desired product as pale yellow solid (Z) -2- (methoxycarbonyl) -3-phenylprop-2-en-1-sulfonic acid sodium salt (compound 2) in 92% yield.
Characterization of the compound (Z) -2- (methoxycarbonyl) -3-phenylpropan-2-ene-1-sulfonate sodium, the results are shown in figures 3-4, and figure 3 is a nuclear magnetic resonance hydrogen spectrum of the (Z) -2- (methoxycarbonyl) -3-phenylpropan-2-ene-1-sulfonate sodium; FIG. 4 is a nuclear magnetic resonance carbon spectrum of sodium (Z) -2- (methoxycarbonyl) -3-phenylprop-2-en-1-sulfonate.
Example 3
(1) In a 10mL Schlenk tube, 0.4mmol of methyl 3-hydroxy-2-methylenehexanoate, 0.4mmol of sodium bisulfite, 0.004mmol of copper bis (trifluoromethylsulfonyl) imide, 0.004mmol of potassium hexafluorophosphate, 1mL of 1,4 dioxane and 2mL of water were added sequentially, and stirred under argon at 80.+ -. 2 ℃ for 17h, the reaction equation being:
(2) After the completion of the reaction by TLC, the solvent was removed by a vacuum rotary evaporator and the solid was washed with methylene chloride to give the objective product as pale yellow solid (Z) -2- (methoxycarbonyl) hex-2-en-1-sulfonic acid sodium salt (Compound 3) in 90% yield.
Characterization of the compound (Z) -2- (methoxycarbonyl) hex-2-ene-1-sulfonic acid sodium salt, the results are shown in FIGS. 5-6, and FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of (Z) -2- (methoxycarbonyl) hex-2-ene-1-sulfonic acid sodium salt; FIG. 6 is a nuclear magnetic resonance carbon spectrum of sodium (Z) -2- (methoxycarbonyl) hex-2-ene-1-sulfonate.
Examples 4 to 17
Examples 4 to 17 are substantially the same as example 1 described above, except that they are shown in the following table 1:
table 1 comparative differences are performed
Example 18
(1) P-aldehyde benzoic acid was added to a methylene chloride solution at room temperature, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine were added at 0℃and stirred for 30min, after which menthol was added. Stirring and reacting for 12h at room temperature to obtain a reaction mixture; wherein, the mol ratio of the p-aldehyde benzoic acid to the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the 4-dimethylaminopyridine to the menthol is 1:1.3:1.4:1, a step of; the reaction equation is:
(2) The reaction mixture was washed with 1M hydrochloric acid, extracted 3 times with dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, the product was isolated by column chromatography on silica gel with a petroleum ether/ethyl acetate system (80:1) as the developing solvent and the product was menthol 4-formylbenzoate as a colorless liquid in 40% yield.
(3) Dissolving 4-formylbenzoic acid menthol ester, methyl acrylate and triethylene diamine in tetrahydrofuran at room temperature, and stirring for 1 week at room temperature to obtain a reaction mixture; wherein, the mole ratio of the 4-formylbenzoic acid menthol ester, the methyl acrylate and the triethylene diamine is 1:2:0.5; the reaction equation is:
(4) The reaction mixture was purified by column chromatography on petroleum ether and ethyl acetate (PE/ea=30/1) to give menthol 4- (1-hydroxy-2- (methoxycarbonyl) allyl) benzoate as a colorless liquid in 89% yield.
(5) Synthesis of sulfonic acid group acrylic acid group compound
In a 10mL Schlenk tube, 0.4mmol of menthol 4- (1-hydroxy-2- (methoxycarbonyl) allyl) benzoate, 0.4mmol of sodium sulfite, 0.004mmol of calcium bis (trifluoromethylsulfonyl) imide, 0.004mmol of potassium hexafluorophosphate, 1mL of ethanol and 2mL of water were added successively, and the mixture was stirred under argon at 80℃for 18 hours, wherein the reaction equation is:
(6) After completion of the reaction by TLC, the solvent was removed by vacuum rotary evaporator and the solid was washed with dichloromethane to give the desired product as a pale yellow solid, sodium (Z) -3- (4- ((menthol oxy) carbonyl) phenyl) -2- (sulfomethyl) acrylate, yield 90%
Example 19
(1) At room temperature, p-aldehyde benzoic acid was added to a methylene chloride solution, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine were added at 0℃and stirred for 30min, and then cholesterol was added. Stirring and reacting for 12h at room temperature to obtain a reaction mixture; wherein, the mole ratio of the p-aldehyde benzoic acid, the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, the 4-dimethylaminopyridine and the cholesterol is 1:1.3:1.4:1, a step of; the reaction equation is:
(2) The reaction mixture was washed with 1M hydrochloric acid, extracted 3 times with dichloromethane, the organic phases were combined, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, the product was isolated by column chromatography on silica gel with a petroleum ether/ethyl acetate system (80:1) as the developing solvent and the product was cholesterol 4-formylbenzoate as a colorless liquid in 70% yield.
(3) Dissolving 4-formylbenzoic acid cholesterol ester, methyl acrylate and triethylene diamine in tetrahydrofuran at room temperature, and stirring for 1 week at room temperature to obtain a reaction mixture; wherein, the mole ratio of the 4-formylbenzoic acid cholesterol ester, the methyl acrylate and the triethylene diamine is 1:2:0.5; the reaction equation is:
(4) The solvent was removed from the reaction mixture under reduced pressure, and the residue was purified by column chromatography on silica gel using petroleum ether and ethyl acetate (PE/ea=30/1) to give 4- (1-hydroxy-2- (methoxycarbonyl) allyl) benzoate as a white solid in 58% yield.
(5) Synthesis of sulfonic acid group acrylic acid group compound
In a 10mL Schlenk tube, 0.4mmol of cholesterol 4- (1-hydroxy-2- (methoxycarbonyl) allyl) benzoate, 0.4mmol of sodium sulfite, 0.004mmol of calcium bis (trifluoromethylsulfonyl) imide, 0.004mmol of potassium hexafluorophosphate, 1mL of ethanol and 2mL of water were added successively, and the mixture was stirred under argon at 80℃for 18h, wherein the reaction equation is:
(6) After completion of the reaction by TLC, the solvent was removed by a vacuum rotary evaporator and the solid was washed with dichloromethane to give the desired product as a pale yellow solid, sodium (Z) -3- (4- ((cholesteryloxy) carbonyl) phenyl) -2- (sulfomethyl) acrylate in 90% yield.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. The preparation method of the sulfonic acid group acrylic acid salt compound surfactant is characterized by comprising the following steps:
(1) Sequentially adding an allyl alcohol compound, a sulfonation reagent, a catalyst and a ligand into a reaction solvent, and stirring and reacting for 17-19 h under the heating condition of 80+/-2 ℃ in an inert gas atmosphere to obtain a reaction solution; wherein the chemical structural formula of the allyl alcohol compound is shown as the following formula:
wherein R is selected from any one of normal aryl, condensed aryl, heteroaryl, cycloalkyl and linear alkyl; the substituent of the n-aryl benzene ring is selected from any one of methoxy, cyano, nitro, tertiary butyl, fluoro, bromo, chloro, ferrocenyl, trimethylsilane ethynyl, menthol ester and cholesterol ester;
the sulfonation reagent is sodium sulfite or sodium bisulfite;
the ligand is potassium hexafluorophosphate;
(2) Removing the reaction solvent in the reaction liquid, and leaching the obtained solid by using dichloromethane to obtain the sulfonic acrylic acid salt compound surfactant with the chemical structural formula shown in the formula (I):
in the formula (I), R is selected from any one of normal aryl, condensed aryl, heteroaryl, cycloalkyl and linear alkyl; the substituent of the n-aryl benzene ring is selected from any one of methoxy, cyano, nitro, tertiary butyl, fluoro, bromo, chloro, ferrocenyl, trimethylsilane ethynyl, menthol ester and cholesterol ester;
x is selected from one of Me group and Na group.
2. The method according to claim 1, wherein in the step (1), the molar volume ratio of the allyl alcohol compound, the sulfonating agent, the catalyst, the ligand and the reaction solvent is 0.4 to 0.8mmol:0.4 to 0.8mmol: 0.004-0.008 mmol: 0.004-0.008 mmol: 3-6 mL.
3. The method of claim 1, wherein in step (1), the catalyst is selected from any one of calcium bis (trifluoromethylsulfonyl) imide, barium bis (trifluoromethylsulfonyl) imide, magnesium bis (trifluoromethylsulfonyl) imide, and copper bis (trifluoromethylsulfonyl) imide.
4. A method according to claim 3, wherein the catalyst is calcium bis (trifluoromethylsulfonyl) imide.
5. The method of claim 1, wherein in step (1), the reaction solvent is mixed by organic solvent and water in a volume ratio of 1:2; wherein the organic solvent is selected from any one of ethanol, N-dimethylformamide, dimethyl sulfoxide, toluene, xylene, methylene dichloride, acetonitrile, 1, 2-dichloroethane, tetrahydrofuran, 1,4 dioxane and isopropanol.
6. The method of claim 1, wherein in step (1), the inert gas is argon.
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| US20040138433A1 (en) * | 2001-03-12 | 2004-07-15 | Earle Martyn J. | Metal bis-triflimide compounds and methods for synthesis of metal bis-triflimide compounds |
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| CN113166081A (en) * | 2018-11-13 | 2021-07-23 | 诺华股份有限公司 | Compounds and compositions for treating conditions associated with NLRP activity |
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| US20040138433A1 (en) * | 2001-03-12 | 2004-07-15 | Earle Martyn J. | Metal bis-triflimide compounds and methods for synthesis of metal bis-triflimide compounds |
| CN113166081A (en) * | 2018-11-13 | 2021-07-23 | 诺华股份有限公司 | Compounds and compositions for treating conditions associated with NLRP activity |
| CN109704926A (en) * | 2019-01-29 | 2019-05-03 | 南京工业大学 | Anticancer activity molecular skeleton 1,4- enyne compounds and the preparation method and application thereof |
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