CN106588770A - Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone - Google Patents
Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone Download PDFInfo
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- CN106588770A CN106588770A CN201611120909.6A CN201611120909A CN106588770A CN 106588770 A CN106588770 A CN 106588770A CN 201611120909 A CN201611120909 A CN 201611120909A CN 106588770 A CN106588770 A CN 106588770A
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- cyclopropyl
- sulfur ylide
- diphenyl sulfonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/20—Spiro-condensed ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
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Abstract
The invention provides a use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as a sulfur ylide reagent and a method for preparation of four-membered cyclic ketone. The cyclopropyl diphenylsulfonium trifluoromethanesulfonate solves the problem that cyclopropyl diphenylsulfonium tetrafluoroborate as the traditional sulfur ylide reagent used in the synthesis of a four-membered cyclic ketone compound from aldehydes or ketones has large synthesis difficulty, complex operation and an expensive price. Under the same reaction conditions, the reactivity of cyclopropyl diphenylsulfonium trifluoromethanesulfonate is comparable to that of cyclopropyl diphenylsulfonium tetrafluoroborate and thus the cyclopropyl diphenylsulfonium trifluoromethanesulfonate can replace cyclopropyl diphenylsulfonium tetrafluoroborate and be used as a novel sulfur ylide reagent.
Description
Technical field
The present invention relates to a kind of purposes of cyclopropyl diphenyl sulfonium fluoroform sulphonate, specifically cyclopropyl diphenyl
Application and a kind of method that prepare quaternary cyclic ketones of the sulfonium fluoroform sulphonate as sulfur ylide reagent in quaternary cyclic ketones is prepared.
Background technology
Cyclopropyl sulfur ylide reagent is the key reagents for synthesizing four-membered ring ketone compounds by aldehydes or ketones, in tradition side
Generally using cyclopropyl diphenyl sulfonium tetrafluoroborate as cyclopropyl sulfur ylide reagent in method, but the reagent is expensive,
And commercially a large amount of supplies.This is a kind of expensive mainly due to silver tetrafluoroborate and the easily rotten examination of deliquescence
Agent so that the building-up process complex operation of cyclopropyl diphenyl sulfonium tetrafluoroborate, difficulty are big, limit the reagent in laboratory
And the extensive application during large-scale production.
Journal of Organic Chemistry, report cyclopropyl in 1988, vol.53, #23p.5571-5573
The preparation method of diphenyl sulfonium fluoroform sulphonate, its structural formula is：
Molecular formula is C16H15F3O3S2, molecular weight is 376.As there is cyclopropyl diphenyl sulfonium fluoroform sulphonate light to float
White effect, which is typically used as photo-acid generator (Jin-Baek Kim, Ji-Hyun Jang, Hyun-Woo, et
al.Photobleaching photoacid generator.Journal of Photopolymer Science and
Technology,2001,14(3),341-344；6541179), at present U.S.Patent not yet has cyclopropyl diphenyl sulfonium three
Report of the fluorine mesylate as cyclopropyl sulfur ylide reagent.
The content of the invention
An object of the present invention is to provide cyclopropyl diphenyl sulfonium fluoroform sulphonate as sulfur ylide reagent in system
Application in standby quaternary cyclic ketones, with solve traditional sulfur ylide reagent cyclopropyl diphenyl sulfonium tetrafluoroborate synthesis difficulty it is big,
Complex operation and it is expensive the problems such as.
The second object of the present invention is to provide a kind of method for preparing quaternary cyclic ketones, to solve using traditional sulfur ylide examination
The problems such as agent cyclopropyl diphenyl sulfonium tetrafluoroborate is expensive.
What an object of the present invention was realized in：
Application of the cyclopropyl diphenyl sulfonium fluoroform sulphonate as sulfur ylide reagent.
Application of the cyclopropyl diphenyl sulfonium fluoroform sulphonate as sulfur ylide reagent in quaternary cyclic ketones is prepared.
The molecular formula of cyclopropyl diphenyl sulfonium fluoroform sulphonate is C16H15F3O3S2, molecular weight is 376, and structural formula is：
According to Journal of Organic Chemistry, the preparation method of 1988, vol.53, #23p.5571-5573
Synthesis cyclopropyl diphenyl sulfonium fluoroform sulphonate, the reagent for being used are mainly：Trimethylsilyl trifluoromethanesulfonate, diphenyl
Sulfoxide, cyclopropyl magnesium bromide.20g (0.099mol) diphenyl sulfoxide is dissolved in freshly prepd dichloromethane, -78 DEG C are down to,
Then 26.4g (0.119mol) Trimethylsilyl trifluoromethanesulfonate is slowly dropped in reaction system, is kept for -78 DEG C and continue to stir
Mix 10 minutes, be then slowly warmed up to 0 DEG C and stir 30 minutes, then cool to -78 DEG C again, by the cyclopropyl of 100mL 2.0M
Magnesium bromide is added drop-wise at reaction system, -78 DEG C and reacts 30min, is then slowly warmed up to 0 DEG C, continues reaction 30min.Question response
Finish, reaction is quenched with the dilute trifluoromethanesulfonic acid aqueous solutions of 300mL, add 200mL chloroform extractions three times, merge organic faciess, then
With anhydrous sodium sulfate drying, rotate removing solvent and obtain white solid, product is obtained with recrystallisation from isopropanol.1HNMR(400MHz,
CDCl3), δ:1.50-1.42(m,2H)；1.62-1.74(m,2H)；3.90-3.80(m,1H)；7.75-7.64(m,6H)；
8.00-7.95(m,4H)
Using cyclopropyl diphenyl sulfonium fluoroform sulphonate as sulfur ylide reagent, can be with 4-Boc- piperidones, tetrahydrochysene pyrrole
Mutter ketone, 4-chloro-benzaldehyde, 2-(Trifluoromethyl) benzaldehyde, to 2,5- dimethoxy-4 's-aldehyde such as tolyl aldehyde and benzophenone or
Reactive ketone generates corresponding quaternary cyclic ketones, and the yield of gained quaternary cyclic ketones is above 55%.
What the second object of the present invention was realized in：
A kind of method for preparing quaternary cyclic ketones, which adopts cyclopropyl diphenyl sulfonium fluoroform sulphonate to try as sulfur ylide
Agent, with the substrate reactions such as aldehydes or ketones, generates corresponding quaternary cyclic ketones.Specifically, cyclopropyl diphenyl sulfonium fluoroform sulphonate can
With 4-Boc- piperidones, tetrahydro pyrone, 4-chloro-benzaldehyde, 2-(Trifluoromethyl) benzaldehyde, to 2,5- dimethoxy-4 's-methylbenzene
Formaldehyde and benzophenone etc. react, and obtain corresponding quaternary cyclic ketones.
The present invention is substituted as Novel ring propyl group sulfur ylide reagent using cyclopropyl diphenyl sulfonium fluoroform sulphonate and is passed
The cyclopropyl sulfur ylide reagent cyclopropyl diphenyl sulfonium tetrafluoroborate of system, cyclopropyl diphenyl sulfonium fluoroform sulphonate it is anti-
Should be active suitable with cyclopropyl diphenyl sulfonium tetrafluoroborate, can effectively solving cyclopropyl diphenyl sulfonium tetrafluoroborate synthesis hardly possible
Degree is big, complex operation and it is expensive the problems such as.
Specific embodiment
The following example can illustrate in greater detail cyclopropyl diphenyl sulfonium fluoroform sulphonate and exist as sulfur ylide reagent
The application in quaternary cyclic ketones is prepared, but present disclosure is not limited to this.
Embodiment 1
30g (0.083mol) cyclopropyl diphenyl sulfonium fluoroform sulphonate is dissolved in 300mL anhydrous tetrahydro furans, is lowered the temperature
To -40 DEG C, then Deca 91mL concentration is double (TMS) potassamides of 1M thereto；Continue stirring after completion of dropping
Then 16.6g (0.083mol) 4-Boc- piperidones are disposably added reaction system by 5min, and -40 DEG C of reaction 20min are natural
3h is stirred after being warming up to room temperature.Question response is finished, and adds 300mL water quenchings to go out reaction, with ether extraction three times (200mL × 3) and
Merge organic faciess, with organic faciess obtained by anhydrous sodium sulfate drying, be concentrated to give grease.Gained grease is dissolved in into 300mL first
In benzene, 7.78g (0.083mol) LiBF4,80 DEG C of reaction 2h is added to be cooled to room temperature, toluene is removed under reduced pressure, add
300mL water quenchings are gone out reaction, extract three times (200mL × 3) with ether and merge organic faciess, with saturated common salt water washing organic faciess two
Secondary (200mL × 2), with organic faciess obtained by anhydrous sodium sulfate drying, are concentrated to give crude product.Using the separating obtained crude product of silicagel column,
15g products are obtained, yield is 75%.
The reaction equation of the reaction is as follows：
Embodiment 2
Will be 10g (0.10mol) tetrahydro pyrones and 39.6g (0.11mol) cyclopropyl diphenyl sulfonium fluoroform sulphonate molten
In 200mL DMSO, under the conditions of frozen water cooling, 11.2g (0.20mol) KOH is dividedly in some parts, is warmed to room temperature naturally reaction 8h.
Question response is finished, and is added 300mL saturated ammonium chloride solutions that reaction is quenched, is continued to be stirred overnight.It is extracted with ethyl acetate three times
(150mL × 2) merge organic faciess, then with saturated common salt water washing organic faciess twice (75mL × 2), it is dry with anhydrous sodium sulfate
It is dry, it is concentrated to give crude product.Using the separating obtained crude product of silicagel column, 11.2g products are obtained, yield is 80%.
The reaction equation of the reaction is as follows：
Embodiment 3
Will be 14g (0.10mol) 4-chloro-benzaldehydes and 35.9g (0.10mol) cyclopropyl diphenyl sulfonium fluoroform sulphonate molten
In 250mL anhydrous tetrahydro furans, under the conditions of frozen water cooling, the tetrahydrofuran of Deca 15.7g (0.14mol) potassium tert-butoxide is molten
Liquid, is warmed to room temperature after completion of dropping naturally, after continuing reaction 3h, adds the tetrafluoroborate solution of 1M, continuation to stir at room temperature
Mix 3h.Question response is finished, and adds 300mL ether extraction organic faciess, then eaten with saturated sodium bicarbonate, saturation in reactant liquor respectively
Salt water washing organic faciess, use anhydrous sodium sulfate drying organic faciess, obtain crude product.Using the separating obtained crude product of silicagel column, obtain
15.3g products, yield are 85%.
The reaction equation of the reaction is as follows：
Embodiment 4
By 15g (0.086mol) 2-(Trifluoromethyl) benzaldehydes and 34.2g (0.095mol) cyclopropyl diphenyl sulfonium fluoroform
Sulfonate is dissolved in 250mL anhydrous tetrahydro furans, under the conditions of frozen water cooling, the tetrahydrochysene of Deca 24.2g (0.22mol) potassium tert-butoxide
Tetrahydrofuran solution, is warmed to room temperature after completion of dropping naturally, after continuing reaction 3h, is added the tetrafluoroborate solution of 1M, is continued in room
The lower stirring 3h of temperature.Question response is finished, and adds 300mL ether extraction organic faciess in reactant liquor, then respectively with saturated sodium bicarbonate,
Saturated common salt water washing organic faciess, obtain organic faciess with anhydrous sodium sulfate drying, obtain crude product.It is separating obtained thick using silicagel column
Product, obtain 10.3g products, and yield is 56%.
The reaction equation of the reaction is as follows：
Embodiment 5
By 10g (0.055mol) to 2,5- dimethoxy-4 's-tolyl aldehyde and 20g (0.055mol) cyclopropyl diphenyl
Sulfonium fluoroform sulphonate is dissolved in 200mL anhydrous tetrahydro furans, is cooled to -15 DEG C, Deca 8.4g (0.075mol) potassium tert-butoxide
Tetrahydrofuran solution, is warmed to room temperature after completion of dropping naturally, after continuing reaction 3h, is added the tetrafluoroborate solution of 1M, is continued
3h is stirred at room temperature.Question response is finished, and adds 300mL diethyl ether solutions extraction organic faciess, use saturated carbon respectively in reactant liquor
Sour hydrogen sodium, saturated common salt water washing organic faciess, use anhydrous sodium sulfate drying organic faciess, obtain crude product.Using silica gel post separation institute
Crude product is obtained, 9.8g products are obtained, yield is 80%.
The reaction equation of the reaction is as follows：
Embodiment 6
Will be 10g (0.055mol) benzophenone and 21.8g (0.060mol) cyclopropyl diphenyl sulfonium fluoroform sulphonate molten
In 200mL DMSO, under the conditions of frozen water cooling, 6.2g (0.011mol) KOH is dividedly in some parts, is warmed to room temperature naturally reaction 8h.
Question response is finished, and, organic faciess is washed with saturated sodium carbonate, and uses anhydrous sulfur with n-hexane extraction reactant liquor twice (150mL × 2)
Sour sodium is dried organic faciess, obtains crude product.Using the separating obtained crude product of silicagel column, 10.7g products are obtained, yield is 88%.
The reaction equation of the reaction is as follows：
Comparative example 1～6
Cyclopropyl diphenyl sulfonium fluoroform sulphonate in embodiment 1～6 is replaced with the ring third of corresponding mole respectively
Base diphenyl sulfonium tetrafluoroborate, other reaction conditions and last handling process it is identical with embodiment 1～6 respectively.
Respectively by embodiment 1～6 and cyclopropyl diphenyl sulfonium fluoroform sulphonate and cyclopropyl hexichol in comparative example 1～6
The reactivity of base sulfonium tetrafluoroborate is contrasted, as shown in table 1.
Table 1
Note：Each substrate reactions condition is basically identical with list of references.
In sum, under identical reaction conditions, the reactivity and ring of cyclopropyl diphenyl sulfonium fluoroform sulphonate
Propyl group diphenyl sulfonium tetrafluoroborate quite, can substitute cyclopropyl diphenyl sulfonium tetrafluoroborate and try as new sulfur ylide
Agent, with broad prospect of application.
Claims (3)
1. application of the cyclopropyl diphenyl sulfonium fluoroform sulphonate as sulfur ylide reagent.
2. application according to claim 1, it is characterised in that cyclopropyl diphenyl sulfonium fluoroform sulphonate is vertical as sulfur leaf
Application of the moral reagent in quaternary cyclic ketones is prepared.
3. a kind of method for preparing quaternary cyclic ketones, it is characterised in that using cyclopropyl diphenyl sulfonium fluoroform sulphonate as sulfur
Ylide reagent.
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| CN201611120909.6A CN106588770A (en) | 2016-12-08 | 2016-12-08 | Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116441A (en) * | 2020-01-07 | 2020-05-08 | 浙江工业大学 | Synthesis method and application of sulfo-containing sulfur ylide |
| CN115850140A (en) * | 2022-12-15 | 2023-03-28 | 浙江工业大学 | Inner salt of p-(dimethylsulfonium)benzenesulfonic acid and its preparation method and application |
Citations (2)
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| CN104203916A (en) * | 2012-03-26 | 2014-12-10 | 先正达参股股份有限公司 | N-cyclylamides as nematicides |
| CN105377036A (en) * | 2013-04-30 | 2016-03-02 | 拜耳作物科学股份公司 | Nematicidal N- (phenylcycloalkyl) carboxamides and N- (phenylcycloalkyl) thiocarboxamides |
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2016
- 2016-12-08 CN CN201611120909.6A patent/CN106588770A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104203916A (en) * | 2012-03-26 | 2014-12-10 | 先正达参股股份有限公司 | N-cyclylamides as nematicides |
| CN105377036A (en) * | 2013-04-30 | 2016-03-02 | 拜耳作物科学股份公司 | Nematicidal N- (phenylcycloalkyl) carboxamides and N- (phenylcycloalkyl) thiocarboxamides |
Non-Patent Citations (1)
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| JENNIFER A. DABROWSKI，ET AL.: "Catalytic and Regioselective Ring Expansion of Arylcyclobutanones with Trimethylsilyldiazomethane. Ligand-Dependent Entry to β-Ketosilane or Enolsilane Adducts", 《ORG. LETT.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116441A (en) * | 2020-01-07 | 2020-05-08 | 浙江工业大学 | Synthesis method and application of sulfo-containing sulfur ylide |
| CN111116441B (en) * | 2020-01-07 | 2022-04-08 | 浙江工业大学 | Synthesis method and application of sulfo-containing sulfur ylide |
| CN115850140A (en) * | 2022-12-15 | 2023-03-28 | 浙江工业大学 | Inner salt of p-(dimethylsulfonium)benzenesulfonic acid and its preparation method and application |
| CN115850140B (en) * | 2022-12-15 | 2023-12-05 | 浙江工业大学 | P- (dimethyl sulfonium) benzenesulfonic acid inner salt and preparation method and application thereof |
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