CN116375749A - Trans-alkenyl potassium trifluoroborate and synthesis method thereof - Google Patents
Trans-alkenyl potassium trifluoroborate and synthesis method thereof Download PDFInfo
- Publication number
- CN116375749A CN116375749A CN202310124064.1A CN202310124064A CN116375749A CN 116375749 A CN116375749 A CN 116375749A CN 202310124064 A CN202310124064 A CN 202310124064A CN 116375749 A CN116375749 A CN 116375749A
- Authority
- CN
- China
- Prior art keywords
- alkenyl
- trans
- reaction
- potassium
- borane
- 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.)
- Pending
Links
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 42
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 alkenyl borane Chemical compound 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910000085 borane Inorganic materials 0.000 claims abstract description 28
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 26
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 21
- 239000011591 potassium Substances 0.000 claims abstract description 21
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 18
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims abstract description 15
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 claims description 3
- FMVJYQGSRWVMQV-UHFFFAOYSA-N ethyl propiolate Chemical compound CCOC(=O)C#C FMVJYQGSRWVMQV-UHFFFAOYSA-N 0.000 claims description 3
- LZULAZTXJLWELL-UHFFFAOYSA-N methyl hex-5-ynoate Chemical compound COC(=O)CCCC#C LZULAZTXJLWELL-UHFFFAOYSA-N 0.000 claims description 3
- IMAKHNTVDGLIRY-UHFFFAOYSA-N methyl prop-2-ynoate Chemical compound COC(=O)C#C IMAKHNTVDGLIRY-UHFFFAOYSA-N 0.000 claims description 3
- FWZMWMSAGOVWEZ-UHFFFAOYSA-N potassium;hydrofluoride Chemical compound F.[K] FWZMWMSAGOVWEZ-UHFFFAOYSA-N 0.000 claims description 3
- DEKXRBRDVIJGBU-UHFFFAOYSA-N 2-fluoroethynylbenzene Chemical group FC#CC1=CC=CC=C1 DEKXRBRDVIJGBU-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 19
- 239000006227 byproduct Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 description 14
- CSCPPACGZOOCGX-MICDWDOJSA-N 1-deuteriopropan-2-one Chemical compound [2H]CC(C)=O CSCPPACGZOOCGX-MICDWDOJSA-N 0.000 description 9
- 239000004327 boric acid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- PBIMIGNDTBRRPI-UHFFFAOYSA-N trifluoro borate Chemical compound FOB(OF)OF PBIMIGNDTBRRPI-UHFFFAOYSA-N 0.000 description 4
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- COERJHDMQUPDCV-UHFFFAOYSA-N [K].FB(F)F Chemical compound [K].FB(F)F COERJHDMQUPDCV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910010277 boron hydride Inorganic materials 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- DGLHLIWXYSGYBI-UHFFFAOYSA-N 1-chloro-2-ethynylbenzene Chemical group ClC1=CC=CC=C1C#C DGLHLIWXYSGYBI-UHFFFAOYSA-N 0.000 description 1
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000007832 transition metal-catalyzed coupling reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses trans-alkenyl potassium trifluoroborate and a synthesis method thereof, which comprises the steps of mixing borane, dimethyl sulfide and alpha-pinene for reaction, then adding alkyne for reaction to obtain alkenyl borane, then adding acetaldehyde for reaction to the alkenyl borane, then adding potassium fluohydride for reaction, and finally concentrating, thermosol, filtering and recrystallizing a reaction system in sequence to obtain the trans-alkenyl potassium trifluoroborate. The preparation method has the advantages of high efficiency, mild reaction conditions, convenient operation, simple post-treatment, no need of ultralow temperature and few byproducts. Is suitable for preparing various trans-alkenyl potassium trifluoroborates. And metal reagents and intermediates are not required to be purified, so that the cost is reduced. The compatibility of functional groups is strong, and the universality of the substrate is high.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and relates to a method for synthesizing trans-alkenyl potassium trifluoroborate.
Background
Alkenyl boron reagent is an important source for constructing olefin structure and has very wide application in the fields of organic synthesis, medical molecules and materials. Alkenyl borate and boric acid have poor stability, require low-temperature storage, and have obvious use limitations. And the synthesis of specific trans-alkenyl boron reagents is more complex. The stability of the potassium trifluoroborate is higher, the application range is wider, and the application value of the alkenyl boron reagent can be greatly improved. The key to the synthesis of potassium trans-alkenyl trifluoroborate is the synthesis of trans-alkenyl boric acid or esters of boric acid.
The existing method for synthesizing the trans-alkenyl boron reagent comprises the following steps: starting from trans-olefin halides, the corresponding alkenyl boron reagents are obtained by a grignard reaction or by metal catalysis and then by reaction with boron reagents. After purification, potassium fluorohydride is used for fluorination to obtain trans-alkenyl potassium trifluoroborate. Such methods suffer from the disadvantage that the purification of the alkenyl boron reagent is difficult and that the cis-products are difficult to avoid when the alkenyl boron reagent is prepared (Ref: j. Org. Chem.2010,75,6001).
Another method for synthesizing the trans-alkenyl boron reagent is to perform addition reaction between alkyne and boron reagent to obtain the trans-alkenyl boron reagent. The main alkyne and the boron hydride reagent are subjected to addition reaction with the boron hydride reagent under specific conditions or under the catalysis of transition metal to obtain a trans-alkenyl boron reagent, and after purification, the trans-alkenyl boron reagent is reacted with potassium fluohydride to obtain trans-alkenyl potassium trifluoroborate. Among them, in order to obtain a stereospecific trans-addition product, the borohydride reaction conditions are extremely severe, while the transition metal catalyst is extremely expensive, and it is necessary to purify the reaction product by a column, and it is impossible to directly react with potassium fluoroborate by a simple process.
In the patent CN201410389205, a trans-alkenyl boron reagent is obtained by reacting acetylene with boron tribromide at a low temperature, and then potassium fluoride or potassium fluoborate is added into the system to prepare the trans-bromovinyl potassium trifluoroborate by a one-pot method. A series of trans-alkenyl potassium trifluoroborates were then prepared by a transition metal catalyzed coupling reaction with different types of boric acid. According to the method, different types of trans-alkenyl potassium trifluoroborates are indirectly prepared through derivatization, the process is complex, transition metal and boric acid are used, the cost is increased, and the expansion of the trans-alkenyl potassium trifluoroborates is limited by the activity of a coupling reaction, so that the method is not beneficial to popularization.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide trans-alkenyl potassium trifluoroborate and a synthesis method thereof.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
a process for synthesizing trans-alkenyl potassium trifluoroborate includes such steps as mixing borane, dimethyl sulfide and alpha-pinene, adding alkyne to obtain alkenyl borane, adding acetaldehyde to alkenyl borane, adding potassium fluohydride to react, concentrating, thermosol, filtering and recrystallizing.
Specifically, the molar ratio of the borane, the dimethyl sulfide, the alpha-pinene, the alkyne, the acetaldehyde and the potassium fluohydride is 1 (1.5-2.5): 1 (35-45): 3-5.
Specifically, the molar ratio of the borane, the dimethyl sulfide, the alpha-pinene, the alkyne, the acetaldehyde and the potassium fluohydride is 1:2:1:40:4.
Specifically, the alkyne includes phenylacetylene, fluorophenylacetylene, p-tolylene, p-methoxyphenylacetylene, o-chlorophenylacetylene, methyl propiolate, ethyl propiolate, methyl 5-hexynoate and 4-benzyloxy-1-butene-1-yne.
Further, the method specifically comprises the following steps:
step 1: under the condition of nitrogen, borane and dimethyl sulfide are added into tetrahydrofuran solution of alpha-pinene at the temperature of minus 5 ℃ to 5 ℃ in a dropwise manner, and stirring reaction is carried out at room temperature to obtain (Ipc) 2 The BH solution is used as a solution,
step 2: the temperature of the system is reduced to minus 50 to minus 30 ℃, alkyne is added, and the temperature is kept between minus 50 and minus 30 ℃ for reaction to obtain alkenyl borane, and the alkenyl borane is stirred at room temperature;
step 3: dropwise adding acetaldehyde into the system in the step 2 at the temperature of between 5 and 5 ℃, carrying out reflux reaction at the temperature of between 30 and 50 ℃, then adding an aqueous solution of potassium fluohydride at the temperature of between 5 and 5 ℃ and stirring at room temperature, concentrating the reaction system into solid in a water bath, adding acetone into the obtained crude product for hot dissolution, carrying out hot filtration, concentrating the filtrate into solid, adding diethyl ether or tert-butyl methyl ether for pulping, and recrystallizing to obtain trans-alkenyl potassium trifluoroborate.
Specifically, the stirring time in the step 1 is 0.5-1.5 h.
Specifically, in the step 2, the reaction time is 2-4 h, and the stirring time is 11-13 h.
Specifically, the reaction time in the step 3 is 17-19 h, and the stirring time is 11-13 h.
Specifically, the temperature at the time of concentration of the water bath in step 3 was 50 ℃.
The invention also discloses trans-alkenyl potassium trifluoroborate synthesized by the synthesis method of the trans-alkenyl potassium trifluoroborate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The one-pot method has the advantages of high efficiency, mild reaction condition, convenient operation, simple post-treatment, no need of ultralow temperature and less byproducts. Is suitable for preparing various trans-alkenyl potassium trifluoroborates.
(2) And metal reagents and intermediates are not required to be purified, so that the cost is reduced.
(3) The conditions and temperature are mild, the compatibility of functional groups is strong, and the universality of the substrate is high.
Detailed Description
The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention, in order to better understand the essential characteristics of the present invention.
The method for synthesizing trans-alkenyl potassium trifluoroborate comprises the steps of mixing borane, dimethyl sulfide and alpha-pinene for reaction, then adding alkyne for reaction to obtain alkenyl borane, then adding acetaldehyde for reaction to the alkenyl borane, then adding potassium fluohydride for reaction, and finally concentrating, thermosol, filtering and recrystallizing a reaction system in sequence to obtain trans-alkenyl potassium trifluoroborate. The reaction formula of the invention is as follows:
the method specifically comprises the following steps:
step 1: under the condition of nitrogen, borane and dimethyl sulfide are added into tetrahydrofuran solution of alpha-pinene at the temperature of minus 5 ℃ to 5 ℃ in a dropwise manner, and stirring reaction is carried out at room temperature to obtain (Ipc) 2 The BH solution is used as a solution,
step 2: the temperature of the system is reduced to minus 50 ℃ to minus 30 ℃, alkyne is added to keep the temperature of minus 50 ℃ to minus 30 ℃ for reaction to obtain alkenyl borane, and the alkenyl borane is stirred at room temperature;
step 3: dropwise adding acetaldehyde into the system in the step 2 at the temperature of between 5 and 5 ℃, carrying out reflux reaction at the temperature of 40 ℃, then adding an aqueous solution of potassium fluohydride at the temperature of between 5 and 5 ℃ and stirring at room temperature, finally concentrating the reaction system to solid in a water bath, adding acetone into the obtained crude product for hot dissolution, carrying out hot filtration, concentrating the filtrate to solid, adding diethyl ether or tert-butyl methyl ether for pulping, and carrying out recrystallization to obtain trans-alkenyl potassium trifluoroborate.
The invention adopts (Ipc) 2 BH is used as a borohydride reagent, cis-trans selectivity is controlled through steric hindrance of alpha-pinene, alkenyl boric acid is prepared by adding alkyne, a trans-addition product can be obtained in a three-dimensional single mode, and the preparation method has wide functional group compatibility. The corresponding borate is obtained by using acetaldehyde as an oxidizing agent, while avoiding the formation of by-products. Then reacts with potassium fluoborate to obtain trans-alkenyl potassium trifluoroborate. And the alpha-pinene and the ethanol in the system are removed in the beating process of diethyl ether or tert-butyl methyl ether. The whole reaction process can be completed by a one-pot method.
The trans-alkenyl potassium trifluoroborate olefin substituent comprises phenyl, p-fluorophenyl, p-methylphenyl, p-methoxyphenyl, o-chlorophenyl, methyl formate, ethyl formate, methyl butyrate and 2-benzyloxy ethyl.
Example 1
The embodiment provides a synthesis method of trans-alkenyl potassium trifluoroborate, which comprises the following steps:
step 1: under the condition of nitrogen, borane and dimethyl sulfide (30 mmol) are added dropwise into tetrahydrofuran solution of alpha-pinene (60 mmol) at 0 ℃ and stirred at room temperature for 1h to react to obtain (Ipc) 2 BH solution during which a large amount of white solid precipitated.
Step 2: the temperature of the system is reduced to-40 ℃, alkyne (30 mmol) is added, and the temperature is kept at-40 ℃ for 3 hours to obtain alkenyl borane, and the alkenyl borane is stirred for 12 hours at room temperature;
step 3: acetaldehyde (24 mL) is added dropwise into the system in the step 2 at the temperature of 0 ℃, reflux reaction is carried out for 18h at the temperature of 40 ℃, then aqueous solution (27 mL) of potassium fluohydride (120 mmol) is added at the temperature of 0 ℃ and stirred for 12h at the room temperature, finally the reaction system is concentrated to solid in a water bath at the temperature of 50 ℃, acetone (50 mL) is added into the obtained crude product to be heated for dissolution, the filtrate is concentrated to solid after hot filtration, diethyl ether or tert-butyl methyl ether is added for pulping, and trans-alkenyl potassium trifluoroborate is obtained through recrystallization.
The preparation of (E) -styryl potassium trifluoroborate in this example, the corresponding alkyne was phenylacetylene, gave 4.9g (78% yield) as a white solid. 1 H NMR(400MHz,acetone-d 6 ):δ7.21(d,J＝7.2Hz,2H),7.09(t,J＝7.6Hz,2H),6.95(t,J＝7.2Hz,1H),6.52(d,J＝18.4Hz,1H),6.16-6.23(m,1H).
Example 2
This example differs from example 1 in that (E) -potassium p-fluorostyryl trifluoroborate was prepared, the corresponding alkyne being p-fluorophenylacetylene, giving 4.7g of a white solid (69% yield). 1 H NMR(400MHz,acetone-d 6 ):δ7.36-7.40(m,2H),7.01(t,J＝8.8Hz,2H),6.65(d,J＝18.4Hz,1H),6.24-6.32(m,1H).
Example 3:
this example differs from example 1 in that (E) -para-methylstyrene potassium trifluoroborate is prepared, the corresponding alkyne being para-methylstyreneAlkyne gave 4.5g (67% yield) of a white solid. 1 H NMR(300MHz,acetone-d 6 ):δ7.22(d,J＝6.6Hz,2H),7.03(d,J＝6.6Hz,2H),6.60(d,J＝19.8Hz,1H),6.25(d,J＝22.5Hz,1H),2.25(s,3H).
Example 4:
this example differs from example 1 in that (E) -potassium p-methoxystyryl trifluoroborate was prepared, and the corresponding alkyne was p-methoxyphenylacetylene, giving 4.5g of a white solid (56% yield). 1 H NMR(300MHz,acetone-d 6 ):δ7.25(d,J＝8.4Hz,2H),6.80(d,J＝8.4Hz,2H),6.50-6.54(m,1H),6.21-6.25(m,1H),3.75(s,3H).
Example 5:
this example differs from example 1 in that (E) -potassium o-chlorostyryl trifluoroborate was prepared, the corresponding alkyne being o-chloroacetylene, giving 3.5g (48% yield) of a white solid. 1 H NMR(400MHz,acetone-d 6 ):δ7.65(d,J＝6.8Hz,1H),7.31(d,J＝7.6Hz,1H),7.23(t,J＝7.6Hz,1H),7.06-7.14(m,2H),6.39-6.46(m,1H).
Example 6:
this example differs from example 1 in that potassium (E) - (3-methoxy-3-oxo-prop-1-en-1-yl) trifluoroborate was prepared, the corresponding alkyne being methyl propiolate, giving 3.0g as a white solid (52% yield). 1 H NMR(300MHz,acetone-d 6 ):δ7.09(d,J＝21.6Hz,1H),6.11(d,J＝18.0Hz,1H),3.76(s,3H).
Example 7:
this example differs from example 1 in that potassium (E) - (3-ethoxy-3-oxoprop-1-en-1-yl) trifluoroborate was prepared, the corresponding alkyne being ethyl propiolate, giving 2.5g (40% yield) as a white solid. 1 H NMR(300MHz,acetone-d 6 ):δ7.04-7.10(m,1H),6.09(d,J＝18.0Hz,1H),4.19-4.25(m,2H),1.33-1.38(m,3H).
Example 8:
this example differs from example 1 in that potassium (E) - (6-methoxy-6-oxo-hex-1-en-1-yl) trifluoroborate was prepared, corresponding alkyne as methyl 5-hexynoate, yielding 4.0g (57% yield) as a white solid. 1 H NMR(400MHz,acetone-d 6 ):δ5.52-5.62(m,1H),5.26(d,J＝13.6Hz,1H),3.48(s,3H),2.14(t,J＝7.6Hz,2H),1.82-1.87(m,2H),1.46-1.53(m,2H).
Example 9:
unlike example 1, potassium (E) - (4-benzyloxy-1-buten-1-yl) trifluoroborate was prepared, corresponding alkyne was 4-benzyloxy-1-buten-1-yne, yielding 3.3g (41% yield) of a white solid. 1 H NMR(400MHz,acetone-d 6 ):δ7.33-7.39(m,4H),7.26-7.29(m,1H),5.68-5.74(m,1H),5.47-5.53(m,1H),4.51(s,2H),3.47(t,J＝7.2Hz,2H),2.27(q,J＝7.2Hz,2H).
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing trans-alkenyl potassium trifluoroborate is characterized by comprising the steps of mixing borane, dimethyl sulfide and alpha-pinene for reaction, then adding alkyne for reaction to obtain alkenyl borane, then adding acetaldehyde for reaction to the alkenyl borane, then adding potassium fluohydride for reaction, and finally concentrating, thermosol, filtering and recrystallizing a reaction system in sequence to obtain trans-alkenyl potassium trifluoroborate.
2. The method for synthesizing trans-alkenyl potassium trifluoroborate according to claim 1, wherein the molar ratio of borane, dimethyl sulfide, alpha-pinene, alkyne, acetaldehyde and potassium fluorohydride is 1 (1.5-2.5): 1 (35-45): 3-5).
3. The method for synthesizing trans-alkenyl potassium trifluoroborate according to claim 1, wherein the molar ratio of borane, dimethyl sulfide, α -pinene, alkyne, acetaldehyde, potassium fluorohydride is 1:2:1:40:4.
4. The method of synthesizing trans-alkenyltrifluoropotassium borate as claimed in claim 1, wherein the alkyne comprises phenylacetylene, fluorophenylacetylene, p-tolylene, p-methoxyphenylacetylene, o-chlorophenylacethylene, methyl propiolate, ethyl propiolate, methyl 5-hexynoate and 4-benzyloxy-1-butene-1-yne.
5. The method for synthesizing trans-alkenyl potassium trifluoroborate as claimed in claim 2, comprising the following steps:
step 1: under the condition of nitrogen, borane and dimethyl sulfide are added into tetrahydrofuran solution of alpha-pinene at the temperature of minus 5 ℃ to 5 ℃ in a dropwise manner, and stirring reaction is carried out at room temperature to obtain (Ipc) 2 The BH solution is used as a solution,
step 2: the temperature of the system is reduced to minus 50 to minus 30 ℃, alkyne is added, and the temperature is kept between minus 50 and minus 30 ℃ for reaction to obtain alkenyl borane, and the alkenyl borane is stirred at room temperature;
step 3: dropwise adding acetaldehyde into the system in the step 2 at the temperature of between 5 and 5 ℃, carrying out reflux reaction at the temperature of between 30 and 50 ℃, then adding an aqueous solution of potassium fluohydride at the temperature of between 5 and 5 ℃ and stirring at room temperature, concentrating the reaction system into solid in a water bath, adding acetone into the obtained crude product for hot dissolution, carrying out hot filtration, concentrating the filtrate into solid, adding diethyl ether or tert-butyl methyl ether for pulping, and recrystallizing to obtain trans-alkenyl potassium trifluoroborate.
6. The method for synthesizing trans-alkenyl potassium trifluoroborate as defined in claim 5, wherein the stirring time in the step 1 is 0.5-1.5 h.
7. The method for synthesizing trans-alkenyl potassium trifluoroborate as defined in claim 5, wherein in the step 2, the reaction time is 2-4 hours and the stirring time is 11-13 hours.
8. The method for synthesizing trans-alkenyl potassium trifluoroborate as defined in claim 5, wherein the reaction time in the step 3 is 17-19 hours and the stirring time is 11-13 hours.
9. The method of synthesizing trans-alkenyl potassium trifluoroborate as defined in claim 5, wherein the concentration in the water bath in step 3 is performed at a temperature of 50 ℃.
10. Trans-alkenyl potassium trifluoroborate synthesized according to the synthesis method of trans-alkenyl potassium trifluoroborate as claimed in any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310124064.1A CN116375749A (en) | 2023-02-16 | 2023-02-16 | Trans-alkenyl potassium trifluoroborate and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310124064.1A CN116375749A (en) | 2023-02-16 | 2023-02-16 | Trans-alkenyl potassium trifluoroborate and synthesis method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116375749A true CN116375749A (en) | 2023-07-04 |
Family
ID=86970139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310124064.1A Pending CN116375749A (en) | 2023-02-16 | 2023-02-16 | Trans-alkenyl potassium trifluoroborate and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116375749A (en) |
-
2023
- 2023-02-16 CN CN202310124064.1A patent/CN116375749A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112898192B (en) | Preparation method of N-acyl indole compound | |
| CN114409515B (en) | Preparation method of gem-difluoroolefin compound | |
| CN115894329B (en) | Synthesis method of indole derivative containing 2-thiocyano-3-aryl by axial chirality | |
| US8513465B2 (en) | Potassium organotrifluoroborate derivative and a production method therefor | |
| CN112321467A (en) | Preparation method of (2S,3R) -p-methylsulfonylphenylserine ethyl ester | |
| CN116375749A (en) | Trans-alkenyl potassium trifluoroborate and synthesis method thereof | |
| CN113651827B (en) | Preparation of pyrano [2,3-b]Process for preparing indol-2-ones | |
| CN111072450B (en) | Synthesis method of allyl alcohol derivative | |
| JPH0476996B2 (en) | ||
| CN114524815A (en) | 8-alkoxy purine derivative and preparation method and application thereof | |
| EP1002788B1 (en) | Process for preparing halogenated phenylmalonates | |
| US6489526B2 (en) | Method for synthesis of hydrocarbyl bridged indenes | |
| CN114213373B (en) | Synthesis method of dibenzofuran derivative | |
| CN115160162B (en) | Asymmetric hydrogenation method of alpha-amino beta-keto ester | |
| CA2867936C (en) | Industrial method for manufacturing high-purity methiozolin | |
| CN115260103B (en) | Preparation method of 4,5-dihalogen-1- (difluoromethyl) -1H-imidazole | |
| CN112811974B (en) | Novel aryl trifluoroethylene synthesized by arylation reagent and preparation method thereof | |
| CN116410218A (en) | Synthesis method of monofluoro alkenyl silicon | |
| JP4807549B2 (en) | Siloxanes, silanols and silanes, and methods for producing the same | |
| WO2000056691A1 (en) | Synthesis of vapol ligands | |
| JPH0637449B2 (en) | Process for producing optically active atenolol and its intermediates | |
| CN116986969A (en) | Synthesis method of fluoroallyl alcohol | |
| CN118146251A (en) | Preparation method of dibenzyl silane compound promoted by visible light | |
| JP2662162B2 (en) | Method for producing 3-alkylpyrrole | |
| CN116574072A (en) | Method for preparing 2, 5-diaryl substituted furan |
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 |