CN114163364A - 2-methoxy allyl sulfonic ester and its synthesis method - Google Patents
2-methoxy allyl sulfonic ester and its synthesis method Download PDFInfo
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- CN114163364A CN114163364A CN202111474604.6A CN202111474604A CN114163364A CN 114163364 A CN114163364 A CN 114163364A CN 202111474604 A CN202111474604 A CN 202111474604A CN 114163364 A CN114163364 A CN 114163364A
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- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 150000002148 esters Chemical class 0.000 title description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- -1 allyl sulfonate Chemical compound 0.000 claims abstract description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 13
- XXROGKLTLUQVRX-UHFFFAOYSA-N hydroxymethylethylene Natural products OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 12
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000010791 quenching Methods 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000004809 thin layer chromatography Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 4
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VKERTODBIWZOJC-ZDUSSCGKSA-N (1s)-1-hydroxy-10-methoxy-2,9-dihydro-1h-cyclopenta[b]carbazol-3-one Chemical compound C12=CC=CC=C2NC2=C1C=C1C(=O)C[C@H](O)C1=C2OC VKERTODBIWZOJC-ZDUSSCGKSA-N 0.000 description 2
- MALRJHQIKRJCMN-UHFFFAOYSA-N 3-bromo-2-methoxyprop-1-ene Chemical compound COC(=C)CBr MALRJHQIKRJCMN-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- FWVHWDSCPKXMDB-LSDHHAIUSA-N Febrifugine Chemical compound O[C@@H]1CCCN[C@H]1CC(=O)CN1C(=O)C2=CC=CC=C2N=C1 FWVHWDSCPKXMDB-LSDHHAIUSA-N 0.000 description 2
- UIHLDYLKWIWXAH-UHFFFAOYSA-N Febrifugine Natural products OC1CCNCC1CC(=O)CN2C=Nc3ccccc3C2=O UIHLDYLKWIWXAH-UHFFFAOYSA-N 0.000 description 2
- KKMPSGJPCCJYRV-UHFFFAOYSA-N Nitidine Chemical compound C1=C2C3=[N+](C)C=C4C=C(OC)C(OC)=CC4=C3C=CC2=CC2=C1OCO2 KKMPSGJPCCJYRV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- VQFAIAKCILWQPZ-UHFFFAOYSA-N bromoacetone Chemical compound CC(=O)CBr VQFAIAKCILWQPZ-UHFFFAOYSA-N 0.000 description 2
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- FWVHWDSCPKXMDB-UHFFFAOYSA-N febrifugine dihydrochloride Natural products OC1CCCNC1CC(=O)CN1C(=O)C2=CC=CC=C2N=C1 FWVHWDSCPKXMDB-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- KYITYFHKDODNCQ-UHFFFAOYSA-M sodium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [Na+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 KYITYFHKDODNCQ-UHFFFAOYSA-M 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 229960002647 warfarin sodium Drugs 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical class C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical compound O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 241001643730 Hydrangea sect. Dichroa Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229930003448 Vitamin K Natural products 0.000 description 1
- 240000003248 Zanthoxylum nitidum Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- SHUZOJHMOBOZST-UHFFFAOYSA-N phylloquinone Natural products CC(C)CCCCC(C)CCC(C)CCCC(=CCC1=C(C)C(=O)c2ccccc2C1=O)C SHUZOJHMOBOZST-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019168 vitamin K Nutrition 0.000 description 1
- 239000011712 vitamin K Substances 0.000 description 1
- 150000003721 vitamin K derivatives Chemical class 0.000 description 1
- 229940046010 vitamin k Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/73—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
Abstract
The invention relates to 2-methoxy allyl sulfonate and a synthesis method thereof, wherein the 2-methoxy allyl sulfonate is a new compound, and the synthesis method comprises the following steps: mixing dimethoxy allyl alcohol and sulfonyl chloride in an organic solvent, adding alkali, reacting for 8-12 h at-40 ℃, adding saturated sodium bicarbonate to quench after the reaction is completed, extracting with ethyl acetate, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain 2-methoxy allyl sulfonate. The synthetic method has the advantages of simple operation, mild conditions, cheap and easily-obtained reaction reagents and long-term storage.
Description
Technical Field
The invention relates to the field of organic compounds and synthesis, in particular to 2-methoxy allyl sulfonate and a synthesis method thereof, and especially relates to some applications of the 2-methoxy allyl sulfonate as an introduced acetyl methyl group.
Background
Acetylmethyl groups are ubiquitous in drug molecules and natural products, and are the precursor group for the synthesis of five-membered ring backbones. Such as Warfarin sodium (Warfarin sodium) which has the function of competitively inhibiting vitamin K; an intermediate of febrifugine, a quinazolinone alkaloid, extracted from the roots and leaves of dichroa febrifugine, having antimalarial activity; extracting nitidine B (8-acetylmethyl dihydropiperdine) from root of Zanthoxylum nitidum; a carbazole cyclopentanone natural product claulansine E with anticancer activity. The compound is introduced with acetyl methyl and then is condensed by aldol to construct cyclopentenone, so as to synthesize various valuable drug intermediates.
Haloacetone is an important reagent for introducing an acetyl methyl group, but the haloacetone can only react with a weaker nucleophilic reagent, such as heteroatoms such as active methylene, O and the like. In 2016 Peng Yi reacted alpha-haloketones with beta-dicarbonyl compounds to construct five-membered furan heterocycles (EurJOC,2016, 5169-5179). In 2018, Balogh, Akos takes bromoacetone as a raw material to react with diethyl malonate to introduce acetyl methyl on an active methylene group, and through a series of reactions such as ring closing, reduction and the like, a pyridazinone compound capable of inhibiting plant growth is obtained and is often used as a herbicide. (WO2018015476A)
In 1977 Jacobson synthesized 2-methoxyallyl bromide (JOC,1977,42,2545), which was able to undergo nucleophilic substitution with a stronger nucleophile, such as the carbon ortho to the carbonyl group, and hydrolyzed to yield an acetylmethyl functionality. But the synthesis method has harsh conditions, requires high temperature of 190 ℃, the product is a mixture, the content of 2-methoxy allyl bromide is 60-70%, the stability is poor, and the product has strong stimulation to eyes.
Disclosure of Invention
The invention provides a new compound 2-methoxy allyl sulfonic ester and a synthesis method thereof for solving the defects of the prior art, the method takes the known compound dimethoxy allyl alcohol and sulfonyl chloride as reactants, and the new compound 2-methoxy allyl sulfonic ester is synthesized under the action of solvent and alkali.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a chemical substance 2-methoxyallylsulfonate, having a structural formula shown as C:
wherein R is one of phenyl, p-methylphenyl, p-nitrophenyl, o-nitrophenyl, p-chlorophenyl, o-chlorophenyl, p-bromophenyl, o-bromophenyl, methyl and trifluoromethyl.
The synthesis method of the 2-methoxyallylsulfonate comprises the following steps:
mixing 2-methoxy allyl alcohol and sulfonyl chloride in a solvent, adding alkali, reacting for 8-12 h at-40 ℃, detecting complete reaction by thin layer chromatography, adding saturated sodium bicarbonate for quenching, extracting with ethyl acetate, drying with anhydrous sodium sulfate, concentrating under reduced pressure to obtain 2-methoxy allyl sulfonate,
wherein R is one of phenyl, p-methylphenyl, p-nitrophenyl, o-nitrophenyl, p-chlorophenyl, o-chlorophenyl, p-bromophenyl, o-bromophenyl, methyl and trifluoromethyl.
Preferably, in the step, the molar ratio of the 2-methoxy allyl alcohol A to the sulfonyl chloride B is 1: 1.0-2.0;
preferably, in the step, the base used in the reaction is one or a combination of triethylamine, N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate and potassium bicarbonate.
Preferably, in the step, the reaction temperature is-40 ℃, and the reaction time is 8-12 h.
Preferably, in the step, the reaction temperature is-10-20 ℃, and the reaction time is 10 h.
Preferably, in the step, the solvent used for the reaction is one or a combination of tetrahydrofuran, dichloromethane, chloroform, acetonitrile, 1, 4-dioxane, benzene and toluene.
Further preferably, the method for synthesizing 2-methoxyallyl sulfonate described in 2 comprises the following specific steps:
(1) dissolving 0.44g and 5mmol of substance A of 2-methoxy allyl alcohol and 1.05g and 5.5mmol of substance B of tosyl chloride in 20mL of anhydrous tetrahydrofuran to obtain substance A1;
(2) adding 0.51g and 5mmol of triethylamine into the substance A1, reacting for 8-12 h at-10-40 ℃, detecting by TLC (thin layer chromatography), stopping the reaction when the raw material point disappears, and obtaining a substance B1;
(3) 20mL of a saturated aqueous solution of sodium hydrogencarbonate was added to substance B1, and the mixture was extracted three to five times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and ethyl acetate was recovered by distillation under reduced pressure to obtain a colorless transparent liquid, a novel compound C, i.e., 2-methoxyallylsulfonate.
Preferably, the reaction temperature is-10 to 20 ℃, and the reaction time is 8 to 10 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention takes the known compounds dimethoxy allyl alcohol A and sulfonyl chloride B as reactants, and synthesizes the new compound 2-methoxy allyl sulfonic ester C under the action of solvent and alkali, the synthetic route is simple, the operation is simple and convenient, the preparation process is easy to control, and the reaction process is safe and environment-friendly.
2. The method has the advantages of mild reaction conditions, cheap and easily-obtained reaction reagents, easy separation of products, high yield and no stimulation to operators.
3. The 2-methoxyallyl alcohol sulfonate can introduce the structure of enol methyl ether into an organic compound with stronger reactivity under mild alkaline conditions, and after the reaction is finished, an acetyl methyl functional group can be introduced on the alpha-carbon of a monocarbonyl group or the C, O, N heteroatom of a compound with a stable chemical structure by acid washing.
Detailed Description
The present invention will be further described with reference to the following examples.
The following examples are given for the details of 2-methoxyallyl sulfonate, its synthesis and its application, but the present invention is not limited to the following examples, and reasonable variations of the parameters can be made without departing from the scope of the present invention.
Example 1
In a 50mL round-bottom flask, 0.44g (5mmol) of 2-methoxyallyl alcohol and 1.05g (5.5mmol) of p-toluenesulfonyl chloride were added, and dissolved in 20mL of anhydrous tetrahydrofuran, and 0.51g (5mmol) of triethylamine was added dropwise to the solution, followed by reaction at 40 ℃ for 8 hours and completion of the reaction was detected by thin layer chromatography. Quenched with saturated sodium bicarbonate, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give new compound C, 2-methoxyallylsulfonate (1.10g, 90.9%).
Example 2
In a 50mL round-bottom flask, 0.44g (5mmol) of 2-methoxyallyl alcohol and 1.05g (5.5mmol) of p-toluenesulfonyl chloride were added, and dissolved in 20mL of anhydrous dichloromethane, and DIPEA0.65g (5mmol) was added dropwise, reacted at 30 ℃ for 12 hours and the reaction was checked for completion by thin layer chromatography. Quenched with saturated sodium bicarbonate, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give new compound C (1.15g, 95.0%).
Example 3
In a 50mL round-bottom flask, 0.44g (5mmol) of 2-methoxyallyl alcohol and 1.14g (6mmol) of p-toluenesulfonyl chloride were added, and they were dissolved in 20mL of anhydrous acetonitrile, and 0.69g (5mmol) of potassium carbonate was added to react at 40 ℃ for 10 hours and the reaction was completed by thin layer chromatography. Quenched with saturated sodium bicarbonate, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give new compound C (1.12g, 92.6%).
Example 4
In a 50mL round-bottom flask, 0.44g (5mmol) of 2-methoxyallyl alcohol and 1.14g (6mmol) of p-toluenesulfonyl chloride were added, and they were dissolved in 20mL of anhydrous chloroform, and 1.63g (5mmol) of cesium carbonate was added to react at 35 ℃ for 11 hours and the reaction was checked for completion by thin layer chromatography. Quenched with saturated sodium bicarbonate, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give new compound C (1.07g, 88.4%).
Example 5
In a 50mL round-bottom flask, 0.44g (5mmol) of 2-methoxyallyl alcohol and 1.14g (6mmol) of p-toluenesulfonyl chloride were added, and the mixture was dissolved in 20mL of anhydrous toluene, and 0.53g (5mmol) of sodium carbonate was added to react at 30 ℃ for 12 hours, and the completion of the reaction was detected by thin layer chromatography. Quenched with saturated sodium bicarbonate, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give new compound C (1.05g, 86.7%).
Example 6
In a 50mL round-bottom flask, 0.44g (5mmol) of 2-methoxyallyl alcohol and 1.14g (6mmol) of p-toluenesulfonyl chloride were added, and dissolved in 20mL1, 4-dioxane, 0.40g (5mmol) of pyridine was added dropwise, and the reaction was carried out at 40 ℃ for 10 hours and checked for completion by thin layer chromatography. Quenched with saturated sodium bicarbonate, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give new compound C (1.06g, 87.6%).
Example 7
(1) Dissolving 0.44g and 5mmol of substance A of 2-methoxy allyl alcohol and 1.05g and 5.5mmol of substance B of tosyl chloride in 20mL of anhydrous tetrahydrofuran to obtain substance A1;
(2) adding 0.51g and 5mmol of triethylamine into the substance A1, reacting for 8-12 h at 40 ℃, detecting by TLC (thin layer chromatography), stopping the reaction when the raw material point disappears, and obtaining a substance B1;
(3) to the substance B1, 20mL of a saturated aqueous solution of sodium hydrogencarbonate was added, extraction was carried out three to five times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and ethyl acetate was recovered by distillation under reduced pressure to obtain 1.10g of a colorless transparent liquid as a new compound C, i.e., 2-methoxyallylsulfonate. The yield was 90.9%.
The nuclear magnetic data of the new compound C after NMR detection are as follows:1H NMR(500MHz，CDCl3)δppm 7.80(d，J＝8.5Hz，2H)，7.34(d，J＝8.5Hz，2H)，4.43(s，2H)，4.21(d，J＝2.5Hz，1H)，4.10(d，J＝3Hz，1H)，3.45(s，3H)，2.44(s，3H)。
example 8
(1) Dissolving 0.44g and 5mmol of substance A of 2-methoxy allyl alcohol and 1.05g and 5.5mmol of substance B of tosyl chloride in 20mL of anhydrous tetrahydrofuran to obtain substance A1;
(2) adding 0.51g and 5mmol triethylamine into the substance A1, reacting at 10 deg.C for 8h, detecting by TLC (thin layer chromatography), stopping reaction to obtain substance B1;
(3) to the substance B1, 20mL of a saturated aqueous solution of sodium hydrogencarbonate was added, extraction was carried out three to five times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and ethyl acetate was recovered by distillation under reduced pressure to obtain 1.10g of a colorless transparent liquid as a new compound C, i.e., 2-methoxyallylsulfonate. The yield was 90.9%.
Claims (9)
1. A chemical substance 2-methoxy allyl sulfonate is characterized in that the chemical structural formula is shown as the following structure C:
wherein R is one of phenyl, p-methylphenyl, p-nitrophenyl, o-nitrophenyl, p-chlorophenyl, o-chlorophenyl, p-bromophenyl, o-bromophenyl, methyl and trifluoromethyl.
2. The method for synthesizing 2-methoxyallylsulfonate as set forth in claim 1, comprising the steps of:
mixing 2-methoxy allyl alcohol and sulfonyl chloride in an organic solvent, adding alkali, reacting for 8-12 h at-40 ℃, detecting complete reaction by thin layer chromatography, adding saturated sodium bicarbonate for quenching, extracting with ethyl acetate, drying with anhydrous sodium sulfate, concentrating under reduced pressure to obtain 2-methoxy allyl sulfonate,
wherein R is one of phenyl, p-methylphenyl, p-nitrophenyl, o-nitrophenyl, p-chlorophenyl, o-chlorophenyl, p-bromophenyl, o-bromophenyl, methyl and trifluoromethyl.
3. The method for synthesizing 2-methoxyallylsulfonate according to claim 2, wherein the molar ratio of 2-methoxyallylalcohol A to sulfonyl chloride B in the step is 1:1.0 to 2.0.
4. The method for synthesizing 2-methoxyallyl sulfonate as claimed in claim 2, wherein in the step, the base used in the reaction is one or more selected from triethylamine, N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate and potassium bicarbonate.
5. The method for synthesizing 2-methoxyallylsulfonate according to claim 2, wherein the reaction temperature is-40 to 40 ℃ and the reaction time is 8 to 12 hours.
6. The method for synthesizing 2-methoxyallylsulfonate according to claim 2, wherein the reaction temperature is-10 to 20 ℃ and the reaction time is 10 hours. .
7. The method for synthesizing 2-methoxyallylsulfonate according to claim 2, wherein the solvent used in the reaction is one or more selected from tetrahydrofuran, dichloromethane, chloroform, acetonitrile, 1, 4-dioxane, benzene, and toluene.
8. The method for synthesizing 2-methoxyallylsulfonate as claimed in claim 2, comprising the following steps:
(1) dissolving 0.44g and 5mmol of substance A of 2-methoxy allyl alcohol and 1.05g and 5.5mmol of substance B of tosyl chloride in 20mL of anhydrous tetrahydrofuran to obtain substance A1;
(2) adding 0.51g and 5mmol of triethylamine into the substance A1, reacting for 8-12 h at-10-40 ℃, detecting by TLC (thin layer chromatography), stopping the reaction when the raw material point disappears, and obtaining a substance B1;
(3) 20mL of a saturated aqueous solution of sodium hydrogencarbonate was added to substance B1, and the mixture was extracted three to five times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and ethyl acetate was recovered by distillation under reduced pressure to obtain a colorless transparent liquid, a novel compound C, i.e., 2-methoxyallylsulfonate.
9. The method for synthesizing 2-methoxyallylsulfonate according to claim 8, wherein the reaction temperature is-10 to 20 ℃ and the reaction time is 8 to 10 hours.
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