CN106008282B - The synthetic method of trifluoromethane sulfonic acid ester - Google Patents
The synthetic method of trifluoromethane sulfonic acid ester Download PDFInfo
- Publication number
- CN106008282B CN106008282B CN201610363161.6A CN201610363161A CN106008282B CN 106008282 B CN106008282 B CN 106008282B CN 201610363161 A CN201610363161 A CN 201610363161A CN 106008282 B CN106008282 B CN 106008282B
- Authority
- CN
- China
- Prior art keywords
- sulfonic acid
- acid ester
- trifluoromethane sulfonic
- synthetic method
- triflate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 150000002905 orthoesters Chemical class 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 16
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 claims 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 30
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000004293 19F NMR spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 description 5
- -1 Methyl fluoride sulphonic acid ester Chemical class 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Methanetriol Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 3
- HDPNBNXLBDFELL-UHFFFAOYSA-N 1,1,1-trimethoxyethane Chemical compound COC(C)(OC)OC HDPNBNXLBDFELL-UHFFFAOYSA-N 0.000 description 2
- AVQPKFFKNUZVPK-UHFFFAOYSA-N 3-methylbutyl trifluoromethanesulfonate Chemical compound CC(C)CCOS(=O)(=O)C(F)(F)F AVQPKFFKNUZVPK-UHFFFAOYSA-N 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- NDJBHBQUEAGIOB-UHFFFAOYSA-N propan-2-yl trifluoromethanesulfonate Chemical compound CC(C)OS(=O)(=O)C(F)(F)F NDJBHBQUEAGIOB-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical class C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000008648 triflates Chemical class 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of synthetic method of trifluoromethane sulfonic acid ester, and the synthesis triflate of reaction reagent, in a mild condition high yield is used as using trifluoromethyl sulfonic acid anhydride and ortho esters.Not only reaction temperature is high for the conventional synthesis process of triflate of the present invention, troublesome in poeration, and isolates and purifies difficulty.It can be reacted using the method for the present invention under the conditions of as mild as a dove, available for the unstable triflate for synthesizing some conventional methods and being difficult to synthesize.And unique accessory substance is lower boiling ester in product, it is very easy to remove.
Description
Technical field
The present invention relates to the synthetic method of trifluoromethane sulfonic acid ester, this method can efficiently synthesize a variety of three in a mild condition
Methyl fluoride sulphonic acid ester.
Background technology
Triflate is a kind of reagent highly useful in organic synthesis, is commonly used for alkylating reagent.Due to trifluoro
The strong electron-withdrawing power of mesyl, the conventional alkylating reagent of reactivity ratio, such as chloro thing or high more of alkyl sulfonic ester.
This kind of compound is due to very active, and only Methyl triflate is relatively stable, and other triflates are easy
Eliminate, the side reaction such as rearrangement, it is necessary to synthesize and post-process under mild conditions.This kind of compound boiling point is low simultaneously, rotten
Corrosion is strong, post-processes than relatively hazardous.Therefore the preparation of triflate is always a problem.
The most common synthetic method of triflate is to react to obtain in the presence of alkali using trifluoromethanesulfanhydride anhydride and alcohol
, this method reaction condition can as mild as a dove, but caused salt by-product needs to wash extraction removing, post-processing operation
Extremely cumbersome, product also easily decomposes in this process.
Triflate and silver iodide can be obtained with silver trifluoromethanesulfonate and idoalkane reaction, filter off inorganic salts
The more pure triflate of acquisition, but the method expensive starting materials (T.Gramstad, R.N.Haszeldine,
Journal of the Chemical Society 1956,173-180)。
CF3SO2OAg+CH3l→ CF3SO2OCH3 +Agl
Yield：69%
1973, Beard et al. was using trifluoromethanesulfonic acid and dimethyl suflfate as Material synthesis Methyl triflate, the party
Method reaction temperature is high and raw material has severe toxicity (C.D.Beard, K.Baum, Grakausk.V, Journal ofOrganic
Chemistry 1973,38,3673-3677)。
2CF3SO2OH+(CH3O)2SO2→ CF3SO2OCH3 +H2SO4
Yield:81%
1985, Aubert et al. prepared triflate, the party using trifluoromethanesulfanhydride anhydride and trimethylsilyl ethers
Method equally have half trifluoromethanesulfanhydride anhydride loss (C.Aubert, J.P.Begue, Synthesis-Stuttgart1985,
759-760)。
Ignatyev et al. is using trifluoromethanesulfanhydride anhydride (or trifluoromethanesulfonic acid and chlorobenzoyl chloride) and dimethyl carbonate as raw material
Quantitative is prepared for Methyl triflate.This method yield is higher, takes full advantage of the trifluoromethyl in molecule, but one
The problem of serious is reaction temperature height, time length, is only capable of preparing stable triflate (Ignatyev, N.；Schmidt,
M.；Heider,U.；Sartori,P.；Kucheryna,,WO 2002/098844,EP1399417B1,2002)
We have found that trifluoromethanesulfanhydride anhydride can react with ortho acid methyl esters, trifluoromethanesulfonic acid first is quantitatively formed in a mild condition
Ester, a kind of universal synthesis method of trifluoromethane sulfonic acid ester under temperate condition is developed on this basis.
The ortho esters that this method uses is cheap, easily prepared, nontoxic pollution-free.Using this method, as mild as a dove
Under conditions of can be with the trifluoromethane sulfonic acid ester of the various structures of acquisition of high yield, including unstable trifluoromethanesulfonic acid secondary alcohol
Ester.Meanwhile unique accessory substance is stable carboxylate in product, and many organic reactions are directly used in without purifying can
In, very easily it can also be removed by the method for distillation.
The content of the invention
The invention provides a kind of mild condition, the new route for the trifluoromethane sulfonic acid ester that easy to operate, versatility is good
And method.
The present invention solves the problems, such as the preparation of the trifluoromethanesulfonic acid of stability difference.Trifluoromethanesulfanhydride anhydride can be in temperature with ortho esters
Reacted with the conditions of, obtain the unstable trifluoromethane sulfonic acid ester that conventional method is difficult to obtain.
The present invention relates to a kind of synthetic method of trifluoromethane sulfonic acid ester (I), it is characterized in that with trifluoromethyl sulfonic acid anhydride with
Ortho esters (II) reacts in organic solvent or under the conditions of solvent-free obtains trifluoromethane sulfonic acid ester (I)：
Described trifluoromethane sulfonic acid ester (I) has following structural formula：
Described ortho esters (II) has following structural formula：
Described R1=H, Me, Et, n-Pr；R2=Me, Et, n-Pr, i-Pr (isopropyl), n-Bu, i-Bu (isobutyl group),
S-Bu (tert-butyl group), n-Pent (amyl group), n-Hex (hexyl), c-Pent (cyclopenta), c-Hex (cyclohexyl), n-C2nH4n+1；
The n=5-11；
Ortho esters (II) and trifluoromethanesulfanhydride anhydride react 0.1~5 hour at a temperature of -40 DEG C~50 DEG C, recommendation response 0.1
~0.5 hour.Obtain the mixture of trifluoromethane sulfonic acid ester (I) and carboxylate；
Described compound (II) and the mol ratio of trifluoromethanesulfanhydride anhydride are 1：0.95-1.05；
Described reaction can in organic solvent or solvent-free middle progress, and the organic solvent used is petroleum ether, just
Hexane, dichloromethane, chloroform or carboxylate etc.；
Described organic solvent carboxylate has following structural formula：
Described R3=H, Me, Et, n-Pr；R4=C1-C6 fatty alkyls；
The weight and volume ratio for recommending described compound (II) and organic solvent are 1 gram：1mL~50mL.
The product of the present invention can directly be used or purified by separated.Described distillation reactor can use general
Logical batch reactor or continuous flow reactor.
The present invention is substantially better than known conventional method：
1) raw material is cheap and easily-available, nontoxic pollution-free.And take full advantage of trifluoromethyl.
2) reaction speed is fast.Can low to -40 DEG C at carry out, charging at room temperature finishes reaction and can terminated.Solve
The composition problem of the triflate of stability difference.
3) reaction produces without solid and gas, can be used for continuous flow reactor.
4) product purity is high, and unique accessory substance is stable carboxylate, is used directly for cascade reaction or treats different things alike anti-
Should.
Embodiment
Following embodiments will be helpful to understand the present invention, but be not intended to limit present disclosure.
The synthesis one of the Methyl triflate of embodiment 1 (TfOMe)
Tf2O+HC(OMe)3→TfoMe+HCO2Me
Under ice bath, by trimethyl orthoformate (3.18g, 30mmol) be slowly added into trifluoromethanesulfanhydride anhydride (8.47 g,
In 30mmol), go at 25 DEG C and react, 15 minutes nuclear-magnetisms monitoring, reaction finishes, vacuum distillation obtain Methyl triflate without
Color liquid 9.74g, yield 99%.
TfOMe:b.p.47℃/42mmHg；1H NMR(400MHz,CDCl3)δ4.21(s,3H)；13C NMR(101MHz,
CDCl3) δ 118.7 (q, J=321.2Hz), 61.6；19F NMR(376MHz,CDCl3)δ-74.5(s,3F).
The synthesis two of the Methyl triflate of embodiment 2 (TfOMe)
Tf2O+MeC(OMe)3→TfoMe+MeCO2Me
Under ice bath, by trimethyl orthoacetate (3.60g, 30mmol) be slowly added into trifluoromethanesulfanhydride anhydride (8.47g,
In 30mmol), go at 25 DEG C and react, 15 minutes nuclear-magnetisms monitoring, reaction finishes, vacuum distillation obtain Methyl triflate without
Color liquid 9.65g, yield 98%.
The synthesis of the trifluoromethanesulfonic acid ethyl ester (TfOEt) of embodiment 3
Tf2O+HC(OEt)3→TfOEt+HCO2Et
Under ice bath, by triethyl orthoformate (4.44g, 30mmol) be slowly added into trifluoromethanesulfanhydride anhydride (8.47g,
In 30mmol), go at 25 DEG C and react, 15 minutes nuclear-magnetisms monitoring, reaction finishes, vacuum distillation obtain trifluoromethanesulfonic acid ethyl ester without
Color liquid 10.15g, yield 94%.
TfOEt:b.p.42℃(42mmHg)；1H NMR(400MHz,CDCl3) δ 4.62 (q, J=7.1Hz, 2H), 1.51
(t, J=7.1Hz, 3H)；13C NMR(101MHz,CDCl3) δ 118.6 (q, J=320.8Hz), 74.0,15.2；19F NMR
(376MHz,CDCl3)δ-75.2(s,3F).
The synthesis of the trifluoromethanesulfonic acid N-butyl of embodiment 4
Tf2O+HC(OnBu)3→TfOnBu+HCOOnBu
Under ice bath, by orthoformic acid tri-n-butyl (3.70g, 15mmol) be slowly added into trifluoromethanesulfanhydride anhydride (2.52ml,
In 15mmol), go at 25 DEG C and react, nuclear-magnetism monitoring in 15 minutes, reaction finishes, and vacuum distillation obtains trifluoromethanesulfonic acid N-butyl
Colourless liquid 5.53g, yield 89%.
TfO(n-C4H9):b.p.40℃(4mmHg)；1H NMR(400MHz,CDCl3) δ 4.54 (t, J=6.4Hz, 2H),
1.87-1.74 (m, 2H), 1.47 (dd, J=15.0,7.5Hz, 2H), 0.97 (t, J=7.4Hz, 3H)；13C NMR(101MHz,
CDCl3) δ 118.6 (q, J=320.8Hz), 77.5,31.1,18.3,13.1；19F NMR(376MHz,CDCl3)δ-75.3(s,
3F).
The synthesis of the trifluoromethanesulfonic acid isopropyl ester of embodiment 5 (TfO (i-Pr))
Tf2P+HC(Oi-C3H7)3→TfOi-C3H7+HCO2i-C3H7
Under ice bath, by the isopropyl ester of orthoformic acid three (5.71g, 30mmol) be slowly added into trifluoromethanesulfanhydride anhydride (5.0ml,
In 30mmol), nuclear-magnetism monitoring in 15 minutes, reaction finishes, and vacuum distillation obtains trifluoromethanesulfonic acid isopropyl ester colourless liquid 4.32g,
Yield 75%.
TfO(i-Pr):b.p.25℃(1mmHg)；1H NMR(400MHz,CDCl3)δ5.25-5.19(m,1H),1.52(d,
J=6.3Hz, 7H)；13C NMR(101MHz,CDCl3) δ 118.5 (q, J=320.5Hz), 86.4,23.0；19F NMR
(376MHz,CDCl3)δ-75.9(s,3F).
Trifluoromethanesulfonic acid isopentyl ester (TfO (the i-C of embodiment 65H11)) synthesis
Tf2O+HC(Oi-C5H11)3→TfOi-C5H11+HCO2i-C5H11
Under ice bath, by the isopentyl ester of orthoformic acid three (4.11g, 15mmol) be slowly added into trifluoromethanesulfanhydride anhydride (2.52ml,
In 15mmol), go at 25 DEG C and react, nuclear-magnetism monitoring in 15 minutes, reaction finishes, and vacuum distillation obtains trifluoromethanesulfonic acid isopentyl ester
Colourless liquid 5.98g, yield 90%.
TfO(i-C5H11):b.p.25℃(0.2mmHg)；1H NMR(400MHz,CDCl3) δ 4.57 (t, J=6.5Hz,
2H), 1.82-1.75 (m, 1H), 1.72 (q, J=6.5Hz, 2H), 0.96 (d, J=6.4Hz, 6H)；13C NMR(101MHz,
CDCl3) δ 118.6 (q, J=321.2Hz), 76.3,37.7,24.4,22.0；19F NMR(376MHz,CDCl3)δ-75.0(s,
3F)。
Claims (5)
- A kind of 1. synthetic method of trifluoromethane sulfonic acid ester, it is characterized in that with trifluoromethyl sulfonic acid anhydride with ortho esters (II) organic Trifluoromethane sulfonic acid ester (I) is obtained in solvent or under the conditions of solvent-free：Described trifluoromethane sulfonic acid ester (I) has following structural formula：Described ortho esters (II) has following structural formula：Described R1=H, Me, Et, n-Pr；R2=Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, n-Pent, n-Hex, ring Amyl group, cyclohexyl, n-C2nH4n+1；The n=5-11；Ortho esters (II) and trifluoromethanesulfanhydride anhydride react 0.1~5 hour at a temperature of -40 DEG C~50 DEG C, obtain trifluoromethyl sulphur Acid esters (I)；Described compound (II) and the mol ratio of trifluoromethanesulfanhydride anhydride are 1：0.95-1.05.
- 2. the synthetic method of trifluoromethane sulfonic acid ester as claimed in claim 1, it is characterized in that reaction is in solvent-free middle progress.
- 3. the synthetic method of trifluoromethane sulfonic acid ester as claimed in claim 1, it is characterized in that described organic solvent is oil Ether, n-hexane, dichloromethane, chloroform or carboxylate；Described organic solvent carboxylate has following structural formula：Described R3=H, Me, Et, n-Pr；R4=C1-C6 fatty alkyls.
- 4. the synthetic method of trifluoromethane sulfonic acid ester as claimed in claim 1, it is characterized in that described product is by distillation point From purifying.
- 5. the synthetic method of trifluoromethane sulfonic acid ester as claimed in claim 1, it is characterized in that described reaction is commonly to criticize Carried out in secondary response device or continuous flow reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610363161.6A CN106008282B (en) | 2016-05-27 | 2016-05-27 | The synthetic method of trifluoromethane sulfonic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610363161.6A CN106008282B (en) | 2016-05-27 | 2016-05-27 | The synthetic method of trifluoromethane sulfonic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008282A CN106008282A (en) | 2016-10-12 |
| CN106008282B true CN106008282B (en) | 2018-01-23 |
Family
ID=57094875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610363161.6A Expired - Fee Related CN106008282B (en) | 2016-05-27 | 2016-05-27 | The synthetic method of trifluoromethane sulfonic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008282B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610660A (en) * | 2001-12-21 | 2005-04-27 | 默克专利有限公司 | Method for producing perfluoroalkane sulfonic acid esters and the salts thereof |
| CN103880715A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Method for continuously preparing ethyl trifluoromethanesulfonate |
| JP2015224218A (en) * | 2014-05-28 | 2015-12-14 | セントラル硝子株式会社 | Production method of perfluoroalkylperfluoroalkane sulfonate |
-
2016
- 2016-05-27 CN CN201610363161.6A patent/CN106008282B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610660A (en) * | 2001-12-21 | 2005-04-27 | 默克专利有限公司 | Method for producing perfluoroalkane sulfonic acid esters and the salts thereof |
| CN103880715A (en) * | 2012-12-19 | 2014-06-25 | 张家港市国泰华荣化工新材料有限公司 | Method for continuously preparing ethyl trifluoromethanesulfonate |
| JP2015224218A (en) * | 2014-05-28 | 2015-12-14 | セントラル硝子株式会社 | Production method of perfluoroalkylperfluoroalkane sulfonate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008282A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102319550A (en) | Low-concentration viscoelastic surfactant solution and preparation method thereof | |
| CN101337938B (en) | Method for synthesizing acetate ionic liquid | |
| CN1995030A (en) | Difluoro bezene derivative production method and produced intermediate | |
| CN106008282B (en) | The synthetic method of trifluoromethane sulfonic acid ester | |
| CN103073421A (en) | High-efficiency simple synthetic method for delta-chlorobutyl ester | |
| CN104080791A (en) | Methods of isolating (4-chloro-2-fluoro-3-substituted-phenyl) boronates and methods of using the same | |
| CN106380421B (en) | Synthetic method bent Sha Kubi | |
| JP5209183B2 (en) | Method for producing 2-cyanophenylboronic acid or ester thereof with reduced impurities | |
| TWI758777B (en) | Crystallization of cyclic phosphonate sodium salt and method for producing the same | |
| CN103804414B (en) | For the preparation of rosuvastain calcium midbody compound and prepared the method for rosuvastain calcium by it | |
| CN106916047B (en) | Synthetic method of diaryl acetylene | |
| CN101967075A (en) | Method for synthesizing terminal alkyne compound by using 3-aryl-2,3-dibromopropionic acid | |
| CN105669743B (en) | Method for preparing phosphinic acid/phosphonous acid/phosphate from P (O) -OH compound and arylboronic acid | |
| RU2399624C1 (en) | Fluorine-containing trimethylsilane synthesis method | |
| CN106365962B (en) | The synthetic method of 1,3- dihydroxy -3,7- dimethyl -6- octene-2-ketone | |
| JP5201620B2 (en) | Phosphonium ionic liquid, method for producing biaryl compound and method for using ionic liquid | |
| CN103540324A (en) | Vinyl cyclohexyl methyl ether liquid crystal compounds and preparation method thereof | |
| AU4678699A (en) | Synthesis of aryl boronic acids | |
| CN102898454A (en) | M-methylphenyldiethoxymethylsilane and preparation method thereof | |
| CN102245617A (en) | Method for silylation of monocarboxylic acids | |
| EP3789375B1 (en) | Process for preparing 4-penten-2-ynal | |
| CN103665038A (en) | Carbon-phosphorus chiral dialkyl oxygen phosphine and synthesis method thereof | |
| EP3495374A1 (en) | Simple preparation method for dialkoxypropyl methylphosphonate | |
| CN111533644B (en) | Synthetic method of key intermediate 4-propargyl-2, 3,5, 6-tetrafluorobenzyl alcohol of fluorobenzyl insecticides | |
| CN102105442A (en) | Aqueous methods for making fluorinated sulfonate esters |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180123 |