CN106588731B - The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate - Google Patents
The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate Download PDFInfo
- Publication number
- CN106588731B CN106588731B CN201611120910.9A CN201611120910A CN106588731B CN 106588731 B CN106588731 B CN 106588731B CN 201611120910 A CN201611120910 A CN 201611120910A CN 106588731 B CN106588731 B CN 106588731B
- Authority
- CN
- China
- Prior art keywords
- reaction
- diphenyl sulfonium
- synthetic method
- cyclopropyl
- sulfonium fluoroform
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- 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
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate, including（a）Using 3 halogen, 1 propyl alcohol and trifluoromethanesulfanhydride anhydride as 3 halopropyl triflate of Material synthesis,（b）3 halopropyl triflates and diphenyl sulfide reaction synthesis 3 halopropyl diphenyl sulfonium fluoroform sulphonates and（c）3 halopropyl diphenyl sulfonium fluoroform sulphonates react synthesis cyclopropyl diphenyl sulfonium fluoroform sulphonate with highly basic.The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate of the present invention is easy to operate, reaction condition is mild, high income, it is easy to amplify, and prepared cyclopropyl diphenyl sulfonium fluoroform sulphonate can be used as novel sulfur ylide reagent, during synthesizing quaternary cyclic ketones as substrate using aldehydes or ketones, activity with common tradition sulfur ylide reagent --- the activity of cyclopropyl diphenyl sulfonium tetrafluoroborate is suitable, is with a wide range of applications.
Description
Technical field
The present invention relates to a kind of synthetic methods of sulfur ylide reagent, concretely relate to a kind of cyclopropyl diphenyl sulfonium
The synthetic method of fluoroform sulphonate.
Background technology
Cyclopropyl sulfur ylide reagent is the key reagents that four-membered ring ketone compounds are synthesized by aldehydes or ketones, in tradition side
Generally use cyclopropyl diphenyl sulfonium tetrafluoroborate is as cyclopropyl sulfur ylide reagent in method, but the reagent price is expensive,
And it does not supply largely on the market.It is examination a kind of expensive and that easily deliquescence goes bad this is mainly due to silver tetrafluoroborate
Agent so that the building-up process of cyclopropyl diphenyl sulfonium tetrafluoroborate is complicated for operation, difficulty is big, limits the reagent in laboratory
And the extensive use during large-scale production.
Cyclopropyl diphenyl sulfonium fluoroform sulphonate has photobleaching effect, 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；
U.S.Patent 6541179), but its synthetic method and its be rarely reported as sulfur ylide reagent.
Invention content
It is an object of the invention to provide a kind of synthetic methods of cyclopropyl diphenyl sulfonium fluoroform sulphonate, existing to solve
Have in technology cyclopropyl diphenyl sulfonium tetrafluoroborate as sulfur ylide reagent building-up process it is complicated and be difficult to extensively using etc.
Problem.
The object of the present invention is achieved like this：
A kind of synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate, includes the following steps：
(a) synthesis of 3- halopropyls triflate
At -20 DEG C~25 DEG C, 3- halogen -1- propyl alcohol and acid binding agent are dissolved in reaction dissolvent, delayed at -20 DEG C~0 DEG C
It is slow that trifluoromethanesulfanhydride anhydride is added dropwise, room temperature is warmed naturally to after being added dropwise, reaction is overnight；After reaction, through extracting, washing,
3- halopropyl triflates are obtained after dry and concentration；Reaction equation is as follows：
In reaction equation, X Cl, Br or I；
The molar ratio of 3- halogen -1- propyl alcohol, acid binding agent and trifluoromethanesulfanhydride anhydride is 1: 1~2: 1~2；
(b) synthesis of 3- halopropyls diphenyl sulfonium fluoroform sulphonate
3- halopropyls triflate and diphenyl sulfide are dissolved in reaction dissolvent, 3- halopropyl trifluoromethanesulfonic acids
The molar ratio of ester and diphenyl sulfide be 1: 1~2, at 40 DEG C~80 DEG C back flow reaction for 24 hours~48h；It is down to room after reaction
Temperature, concentration are precipitated solid after adding in ether, filter and wash, dry obtained solid, obtain 3- halopropyl diphenyl sulfonium trifluoros
Mesylate；Reaction equation is as follows：
(c) synthesis of cyclopropyl diphenyl sulfonium fluoroform sulphonate
3- halopropyl diphenyl sulfonium fluoroform sulphonates are dissolved in anhydrous tetrahydro furan or anhydrous ether, are added portionwise
The molar ratio of highly basic, 3- halopropyls diphenyl sulfonium fluoroform sulphonate and highly basic is 1: 1~2, reacts 12h at 0~65 DEG C
~for 24 hours；After the completion of reaction, add in dilute trifluoromethanesulfonic acid aqueous solution and reaction is quenched and post-treated obtains cyclopropyl diphenyl sulfonium three
Fluorine mesylate；Reaction equation is as follows：
In step (a), the acid binding agent is one kind in triethylamine, diisopropyl ethyl amine or pyridine.
In step (a), the molar ratio of the 3- halogen -1- propyl alcohol and acid binding agent is 1: 1.1.
In step (a) and (b), the reaction dissolvent is one kind in dichloromethane, chloroform or 1,2- dichloroethanes.
In step (a), the reaction temperature is -20 DEG C~-10 DEG C.
In step (b), the reaction temperature is 40 DEG C~65 DEG C.
In step (c), the highly basic is one kind in potassium tert-butoxide, sodium tert-butoxide or sodium hydride.
In step (c), the post processing includes with chloroform extraction mixed solution three times, merging organic phase, and with saturation chlorine
Change sodium water solution washing, anhydrous sodium sulfate drying organic phase, concentration adds in ether, there is solid precipitation, filters, and washed with ether
Obtained solid is washed, is dried to obtain crude product, and gained crude product is recrystallized using absolute ethyl alcohol, you can obtain cyclopropyl diphenyl sulfonium
Fluoroform sulphonate.
The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate of the present invention is easy to operate, and reaction condition is mild, yield
Height is easy to amplify.New sulfur can be used as using the obtained cyclopropyl diphenyl sulfonium fluoroform sulphonate of synthetic method of the present invention
Ylide reagent, during synthesizing quaternary cyclic ketones as substrate using aldehydes or ketones, activity and common traditional sulfur ylide
The activity of reagent --- cyclopropyl diphenyl sulfonium tetrafluoroborate quite, solves the synthesis of cyclopropyl diphenyl sulfonium tetrafluoroborate
The problems such as difficulty is big, complicated for operation i.e. expensive, is with a wide range of applications.
Specific embodiment
The present invention is further described in example below, but the invention is not limited in any way.
Following synthetic routes describe the synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate of the present invention, used
Reagent is that analysis is pure or chemical pure and commercially available or pass through organic chemistry filed method system well-known to the ordinarily skilled artisan
It is standby.Following embodiments realize the goal of the invention of the present invention.
Embodiment 1
(a) synthesis of 3- bromopropyls triflate：By 13.9g (0.10mol) 3- bromopropyl alcohols, 8.7g (0.11mol)
Pyridine and 150mL dichloromethane are added in 250mL three-necked flasks, are cooled to 0 DEG C.Under the conditions of being -20 DEG C in stirring, temperature slowly
29.63g (0.105mol) trifluoromethanesulfanhydride anhydride is added dropwise, room temperature is warmed naturally to after being added dropwise, reaction is overnight.Reaction terminates
Afterwards, the dilute hydrochloric acid of a concentration of 0.1mol/L of 30mL is added in into reaction solution, stirring layering extracts organic phase, then use respectively
Aqueous sodium carbonate and saturated sodium-chloride water solution the washing organic phase of 0.1mol/L, and it is organic using anhydrous sodium sulfate drying
Phase is concentrated to give 22g 3- bromopropyl triflates, yield 81%.
Reaction equation is as follows：
(b) synthesis of 3- bromopropyls diphenyl sulfonium fluoroform sulphonate：By 20g (0.074mol) 3- bromopropyl trifluoro methylsulphurs
Acid esters, 13.7g (0.074mol) diphenyl sulfides and 150mL dichloromethane are added in 250mL single-necked flasks, are flowed back at 40 DEG C anti-
Answer 48h.After completion of the reaction, it treats that temperature is cooled to room temperature, concentrates, add in ether, there is solid precipitation, filter and wash institute with ether
Solid is obtained, 30g 3- bromopropyl diphenyl sulfonium fluoroform sulphonates, yield 89% are obtained after dry.
Reaction equation is as follows：
(c) synthesis of cyclopropyl diphenyl sulfonium fluoroform sulphonate：By 25g (0.055mol) 3- bromopropyl diphenyl sulfonium three
Fluorine mesylate and 150mL anhydrous tetrahydro furans are added in 250mL three-necked flasks, are cooled to 0 DEG C, 2.3g is added portionwise and contains ore deposit
The sodium hydrogen (active ingredient 60%) of object oil, reacts for 24 hours at room temperature.After reaction, it is water-soluble that the dilute trifluoromethanesulfonic acids of 200mL are added in
Reaction is quenched in liquid, using 100mL chloroforms extraction mixed solution three times, merges organic phase, and with 75mL saturated sodium-chloride water solutions
Washing, anhydrous sodium sulfate drying organic phase, concentration add in ether, there is solid precipitation, filter, and wash obtained solid with ether,
It is dried to obtain crude product.Gained crude product is recrystallized using absolute ethyl alcohol, obtains 14.5g cyclopropyl diphenyl sulfonium fluoroform sulphonates,
Yield is 70%.
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)
Reaction equation is as follows：
Embodiment 2
Cyclopropyl diphenyl sulfonium fluoroform sulphonate is synthesized in accordance with the following steps, and synthetic route is same as Example 1.
(a) synthesis of 3- chloropropyls triflate：By 9.5g (0.10mol) 3- chloropropyl alcohols, 11.2g (0.11mol)
Triethylamine and 100mL chloroforms are added in 250mL three-necked flasks, are cooled to 0 DEG C.It is slowly added dropwise under the conditions of being -10 DEG C in temperature
31.2g (0.11mol) trifluoromethanesulfanhydride anhydride warms naturally to room temperature after being added dropwise, reaction is overnight.After reaction, to anti-
The dilute hydrochloric acid that a concentration of 0.1mol/L of 30mL are added in solution is answered, stirring layering extracts organic phase, then use 0.1mol/L respectively
Aqueous sodium carbonate and saturated sodium-chloride water solution washing organic phase, and using anhydrous sodium sulfate dry organic phase, be concentrated to give
To 18g3- chloropropyl triflates, yield 79%.
(b) synthesis of 3- chloropropyls diphenyl sulfonium fluoroform sulphonate：By 18g (0.079mol) 3- chloropropyl trifluoro methylsulphurs
Acid esters, 22.2g (0.119mol) diphenyl sulfides and 150mL chloroforms are added in 250mL single-necked flasks, the back flow reaction at 65 DEG C
24h.After completion of the reaction, it treats that temperature is cooled to room temperature, concentrates, add in ether, there is solid precipitation, filter and wash gained with ether
Solid obtains 28g 3- chloropropyl diphenyl sulfonium fluoroform sulphonates, yield 85% after dry.
(c) synthesis of cyclopropyl diphenyl sulfonium fluoroform sulphonate：By 28g (0.068mol) 3- chloropropyl diphenyl sulfonium three
Fluorine mesylate and 150mL anhydrous tetrahydro furans are added in 250mL three-necked flasks, are cooled to 0 DEG C, 13g is added portionwise
(0.136mol) potassium tert-butoxide is reacted for 24 hours at 60 DEG C.After reaction, the dilute trifluoromethanesulfonic acid aqueous solutions of 200mL are added in be quenched instead
Should, using 100mL chloroforms extraction mixed solution three times, merge organic phase, and washed with 75mL saturated sodium-chloride water solutions, it is anhydrous
Sodium sulphate dries organic phase, and concentration adds in ether, there is solid precipitation, filters, and wash obtained solid with ether, is dried to obtain
Crude product.Gained crude product is recrystallized using absolute ethyl alcohol, obtains 13g cyclopropyl diphenyl sulfonium fluoroform sulphonates, yield 51%.
Embodiment 3
Cyclopropyl diphenyl sulfonium fluoroform sulphonate is synthesized in accordance with the following steps, and synthetic route is same as Example 1.
(a) synthesis of 3- iodine propyl triflate：By 25g (0.134mol) 3- iodine propyl alcohol, 26g (0.202mol) two
Diisopropylethylamine and 150mL 1,2- dichloroethanes are added in 250mL three-necked flasks, are cooled to 0 DEG C.In stirring, temperature 0
56.9g (0.202mol) trifluoromethanesulfanhydride anhydride is slowly added dropwise under the conditions of DEG C, warms naturally to room temperature after being added dropwise, reacted
Night.After reaction, the dilute hydrochloric acid of a concentration of 0.1mol/L of 30mL is added in into reaction solution, stirring layering extracts organic
Phase, then organic phase is washed with the aqueous sodium carbonate of 0.1mol/L and saturated sodium-chloride water solution respectively, and using anhydrous slufuric acid
Sodium dries organic phase, is concentrated to give 33g 3- iodine propyl triflates, yield 77%.
(b) synthesis of 3- iodine propyl diphenyl sulfonium fluoroform sulphonate：By 33g (0.104mol) 3- iodine propyl trifluoro methylsulphurs
Acid esters, 38.7g (0.208mol) diphenyl sulfides and 150mL 1,2- dichloroethanes are added in 250mL single-necked flasks, at 80 DEG C
Back flow reaction 36h.After completion of the reaction, it treats that temperature is cooled to room temperature, concentrates, add in ether, have solid precipitation, filter and use ether
Obtained solid is washed, 20g 3- iodine propyl diphenyl sulfonium fluoroform sulphonates, yield 38% are obtained after dry.
(c) synthesis of cyclopropyl diphenyl sulfonium fluoroform sulphonate：By 20g (0.04mol) 3- iodine propyl diphenyl sulfonium three
Fluorine mesylate and 150mL anhydrous ethers are added in 250mL three-necked flasks, are cooled to 0 DEG C, 8.9g (0.08mol) is added portionwise
Sodium tert-butoxide reacts 12h at 25 DEG C.After reaction, the dilute trifluoromethanesulfonic acid aqueous solutions of 200mL are added in and reaction is quenched, used
100mL chloroforms extraction mixed solution three times, merges organic phase, and washed with 75mL saturated sodium-chloride water solutions, anhydrous sodium sulfate
Dry organic phase, concentration add in ether, there is solid precipitation, filter, and wash obtained solid with ether, are dried to obtain crude product.Institute
It obtains crude product to recrystallize using absolute ethyl alcohol, obtains 7.5g cyclopropyl diphenyl sulfonium fluoroform sulphonates, yield 50%.
Embodiment 4
14g (0.10mol) 4-chloro-benzaldehydes and 35.9g (0.10mol) cyclopropyl diphenyl sulfonium fluoroform sulphonate is molten
In 250mL anhydrous tetrahydro furans, under ice water cooling condition, the tetrahydrofuran that 15.7g (0.14mol) potassium tert-butoxide is added dropwise is molten
Liquid is warmed to room temperature naturally after being added dropwise, and after the reaction was continued 3h, adds in the tetrafluoroborate solution of 1M, continues to stir at room temperature
Mix 3h.It treats that reaction finishes, 300mL ether extraction organic phase is added in into reaction solution, then eaten respectively with saturated sodium bicarbonate, saturation
Salt water washing organic phase dries organic phase with anhydrous sodium sulfate, obtains crude product.Using the separating obtained crude product of silicagel column, obtain
15.3g products, yield 85%.
The reaction equation of the reaction is as follows：
Embodiment 5
By 15g (0.086mol) 2-(Trifluoromethyl) benzaldehydes and 34.2g (0.095mol) cyclopropyl diphenyl sulfonium fluoroform
Sulfonate is dissolved in 250mL anhydrous tetrahydro furans, and under ice water cooling condition, the tetrahydrochysene of 24.2g (0.22mol) potassium tert-butoxide is added dropwise
Tetrahydrofuran solution is warmed to room temperature naturally after being added dropwise, and after the reaction was continued 3h, is added in the tetrafluoroborate solution of 1M, is continued in room
The lower stirring 3h of temperature.Treat that reaction finishes, add in 300mL ether extraction organic phase into reaction solution, then respectively with saturated sodium bicarbonate,
Saturated common salt water washing organic phase, is dried to obtain organic phase with anhydrous sodium sulfate, obtains crude product.It is separating obtained thick using silicagel column
Product obtain 10.3g products, yield 56%.
The reaction equation of the reaction is as follows：
Comparative example 1~2
The cyclopropyl diphenyl sulfonium fluoroform sulphonate in embodiment 4 and embodiment 5 is replaced with into corresponding mole respectively
Cyclopropyl diphenyl sulfonium tetrafluoroborate, other reaction conditions and last handling process respectively with 5 phase of embodiment 4 and embodiment
Together.
Respectively by cyclopropyl diphenyl sulfonium fluoroform sulphonate and cyclopropyl diphenyl in embodiment 4,5 and comparative example 1~2
The reactivity of sulfonium tetrafluoroborate is compared, as shown in table 1.
Table 1
Claims (8)
1. a kind of synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate, which is characterized in that include the following steps：
(a) synthesis of 3- halopropyls triflate
At -20 DEG C~25 DEG C, 3- halogen -1- propyl alcohol and acid binding agent are dissolved in reaction dissolvent, slowly dripped at -20 DEG C~0 DEG C
Add trifluoromethanesulfanhydride anhydride, room temperature is warmed naturally to after being added dropwise, reaction is overnight；After reaction, through extracting, washing, drying
And obtain 3- halopropyl triflates after concentration；Reaction equation is as follows：
In reaction equation, X Cl, Br or I；
The molar ratio of 3- halogen -1- propyl alcohol, acid binding agent and trifluoromethanesulfanhydride anhydride is 1: 1~2: 1~2；
(b) synthesis of 3- halopropyls diphenyl sulfonium fluoroform sulphonate
3- halopropyls triflate and diphenyl sulfide are dissolved in reaction dissolvent, 3- halopropyls triflate with
The molar ratio of diphenyl sulfide be 1: 1~2, at 40 DEG C~80 DEG C back flow reaction for 24 hours~48h；It is down to room temperature after reaction, it is dense
Contracting is precipitated solid after adding in ether, filters and wash, dries obtained solid, obtain 3- halopropyl diphenyl sulfonium trifluoro methylsulphurs
Hydrochlorate；Reaction equation is as follows：
(c) synthesis of cyclopropyl diphenyl sulfonium fluoroform sulphonate
3- halopropyl diphenyl sulfonium fluoroform sulphonates are dissolved in anhydrous tetrahydro furan or anhydrous ether, are added portionwise strong
The molar ratio of alkali, 3- halopropyls diphenyl sulfonium fluoroform sulphonate and highly basic be 1: 1~2, at 0~65 DEG C react 12h~
24h；After the completion of reaction, add in dilute trifluoromethanesulfonic acid aqueous solution and reaction is quenched and post-treated obtains cyclopropyl diphenyl sulfonium trifluoro
Mesylate；Reaction equation is as follows：
2. synthetic method according to claim 1, which is characterized in that in step (a), the acid binding agent is triethylamine, two
One kind in diisopropylethylamine or pyridine.
3. synthetic method according to claim 2, which is characterized in that in step (a), the 3- halogen -1- propyl alcohol is with tiing up acid
The molar ratio of agent is 1: 1.1.
4. synthetic method according to claim 1, which is characterized in that in step (a) and (b), the reaction dissolvent is two
One kind in chloromethanes, chloroform or 1,2- dichloroethanes.
5. synthetic method according to claim 1, which is characterized in that in step (a), the reaction temperature for -20 DEG C~-
10℃。
6. synthetic method according to claim 1, which is characterized in that in step (b), the reaction temperature is 40 DEG C~65
℃。
7. synthetic method according to claim 1, which is characterized in that in step (c), the highly basic is potassium tert-butoxide, uncle
One kind in sodium butoxide or sodium hydride.
8. synthetic method according to claim 1, which is characterized in that in step (c), the post processing includes being extracted with chloroform
It takes mixed solution three times, merges organic phase, and washed with saturated sodium-chloride water solution, anhydrous sodium sulfate drying organic phase, concentration,
Ether is added in, there is solid precipitation, is filtered, and obtained solid is washed with ether, is dried to obtain crude product, and gained crude product is used into nothing
Water-ethanol recrystallizes, you can obtains cyclopropyl diphenyl sulfonium fluoroform sulphonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611120910.9A CN106588731B (en) | 2016-12-08 | 2016-12-08 | The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611120910.9A CN106588731B (en) | 2016-12-08 | 2016-12-08 | The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106588731A CN106588731A (en) | 2017-04-26 |
| CN106588731B true CN106588731B (en) | 2018-06-29 |
Family
ID=58597427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611120910.9A Active CN106588731B (en) | 2016-12-08 | 2016-12-08 | The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106588731B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142573A (en) * | 2019-06-28 | 2020-12-29 | 天津药业研究院股份有限公司 | Method for synthesizing triclosan |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4233292A (en) * | 1979-02-07 | 1980-11-11 | Sandoz, Inc. | Cyclopropyl sulfonium salts |
| US10865216B2 (en) * | 2012-09-12 | 2020-12-15 | Merck Sharp & Dohme Corp. | Tricyclic Gyrase inhibitors |
-
2016
- 2016-12-08 CN CN201611120910.9A patent/CN106588731B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Deoxygenation of Sulfoxides Promoted by Electrophilic Silicon Reagents: Preparation of Aryl-Substituted Sulfonium Salts;R.D.Miller 等;《J.Org.Chem》;19881231;第53卷(第23期);第5571-5573页 * |
| Jin-Baek Kim 等.Cyclopropyl-containing Photoacid Generators for Chemically Amplified Resists.《Chemistry Letters》.2003,第32卷(第6期),第554-555页. * |
| Preparation of Cyclopropyldiphenylsulfonium and 2-Methylcyclopropyldiphenylsulfonium Fluoroborate and Their Ylides.Stereochemistry of Sulfur Ylides;Barry M. Trost 等;《Journal of the American Chemical Sociery 》;19730808;第95卷(第16期);第5298-5307页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106588731A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104387311B (en) | A kind of synthetic method of 3-arylseleno benzazolyl compounds | |
| CN102311392A (en) | Synthetic method of azoxystrobin and special intermediate for synthesis | |
| CN101891649B (en) | Novel 3-cyano methyl benzoate preparing method | |
| CN105218453B (en) | Method for preparation of medetomidine with chloroacetone | |
| CN108610324A (en) | A kind of preparation method of sulfuric acid vinyl ester | |
| CN104230821B (en) | The synthetic method of Fluoxastrobin | |
| CN106588731B (en) | The synthetic method of cyclopropyl diphenyl sulfonium fluoroform sulphonate | |
| CN107963994A (en) | A kind of green method for preparing 5 FU 5 fluorouracil | |
| CN105452228A (en) | A novel process for the preparation of febuxostat | |
| CN105601529B (en) | The synthetic method of pretilachlor | |
| CN106588770A (en) | Use of cyclopropyl diphenylsulfonium trifluoromethanesulfonate as sulfur ylide reagent and method for preparation of four-membered cyclic ketone | |
| CN102603508A (en) | Preparation method of 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone and intermediate thereof as well as preparation method of intermediate | |
| CN103288693B (en) | Method for preparing 1-mercaptopyrene and intermediate compound thereof | |
| CN105037298A (en) | Trifluoromethyl substituted continuous quaternary carbon center cyclopropane derivative and synthetic method | |
| CN102786404B (en) | Preparation method for benzil dimethyl ketal | |
| CN102757390B (en) | Method for preparing 2-methoxy-4-diazanyl-5-fluoropyrimidine | |
| CN105541712B (en) | The preparation method of Solifenacin intermediate | |
| CN104478791B (en) | (S) preparation method of-5-R-5-azaspiro [2,4] heptane-6-carboxylic acid | |
| CN104311456B (en) | A kind of preparation method of sulfogaiacol | |
| CN106986907A (en) | For the preparation method for the intermediate for preparing betamethasone | |
| CN106748697A (en) | A kind of preparation method of acetylacetone,2,4-pentanedione beryllium | |
| CN112830892A (en) | Synthesis method of pyridine-3-sulfonyl chloride | |
| CN106957235B (en) | A kind of preparation method of tamoxifen | |
| CN104211652A (en) | Method for preparing plerixafor | |
| CN106220479B (en) | A method of it recycles sevoflurane impurity F (1) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |