CN116640077A - Synthesis method of 1, 1-diseleno olefin compound - Google Patents
Synthesis method of 1, 1-diseleno olefin compound Download PDFInfo
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- CN116640077A CN116640077A CN202310515543.6A CN202310515543A CN116640077A CN 116640077 A CN116640077 A CN 116640077A CN 202310515543 A CN202310515543 A CN 202310515543A CN 116640077 A CN116640077 A CN 116640077A
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- diseleno
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- alkyl
- cycloalkyl
- olefin compound
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- -1 olefin compound Chemical class 0.000 title claims abstract description 72
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 239000003480 eluent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000000266 alpha-aminoacyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 238000004440 column chromatography Methods 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004043 oxo group Chemical group O=* 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 33
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000012467 final product Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 40
- 238000005481 NMR spectroscopy Methods 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 9
- 239000011669 selenium Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Chemical compound C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 6
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 150000005029 thianthrenes Chemical class 0.000 description 2
- NLKLUGVCAPFMIE-UHFFFAOYSA-N 2-(thiophen-2-yldiselanyl)thiophene Chemical compound C=1C=CSC=1[Se][Se]C1=CC=CS1 NLKLUGVCAPFMIE-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 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
- 241000511343 Chondrostoma nasus Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XNERWVPQCYSMLC-UHFFFAOYSA-N phenylpropiolic acid Chemical compound OC(=O)C#CC1=CC=CC=C1 XNERWVPQCYSMLC-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
- C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of a 1, 1-diseleno olefin compound, which comprises the steps of mixing an alkenyl thianthrene salt compound (1 a) and a diseleno ether compound (1 b) with alkali, adding a solvent under the protection of nitrogen, reacting for 5-6 hours at room temperature, and performing post-treatment to obtain a product 1, 1-diseleno olefin compound (1 c); the method has simple operation, mild conditions and no metal catalysis, and the final product can have medium or more yield;
Description
Technical Field
The present invention relates to a method for synthesizing a 1, 1-diseleno olefin compound, namely, a method for efficiently synthesizing a 1, 1-diseleno olefin compound by reacting various alkenyl thianthrene salts with diseleno ether derivatives.
Background
The thianthrene salt is used as a novel direct functional group tool of C-H at present, and has very wide application in reactions such as transition metal catalysis, photochemistry and the like. Thianthrene salts can be classified into aryl thianthrene salts, alkenyl thianthrene salts and alkyl thianthrene salts. The alkenylthianthrene salt, as an electrophilic alkenylating reagent, may be reacted with other reagents such as alkynes, alkenes or some nucleophiles to give the corresponding alkenylated or allylated product. (Angew.chem.int.ed.2020, 59, 5616-5620), (J.am.chem.Soc.2021, 143, 21503-21510).
Selenoalkenes are very important synthetic building blocks in organic synthesis reactions that can be used as intermediates in the production of conjugated olefin products. Seleno olefins can also undergo numerous cross-coupling reactions under transition metal catalysis to synthesize numerous corresponding alkenyl compounds (j. Tetlet.2016,57, 4128-4132), transition metal catalysis such as Pd (chem. Commun.,2015,51,15522-15525), fe (org. Biomol. Chem.,2012,10,798-807), and the like. Selenium-containing heterocycles can also be produced under the action of n-BuLi (J.Org.chem.2007, 72,18,6726-6734). The 1, 1-diseleno alkene can also be used to produce an alkenyl lithium intermediate under the action of n-BuLi, which is very reactive and can undergo a series of nucleophilic reactions (j. Tetlet.1982,33, 3411-3414).
At present, the synthesis of 1, 1-diseleno olefin has little research, and the following two synthesis routes are mainly available at present: (1) Reacting benzaldehyde and its derivative with carbon tetrabromide to obtain 1, 1-dibromo-alkene, and reacting the obtained 1, 1-dibromo-alkene with diselenide and its derivative to obtain the final product (j.tetlet.2016, 57, 4128-4132), (j.org.chem.2002, 51,875-8.); (2) The final product (org. Lett.2018,20, 3678-3681) is obtained by reacting phenylethynyl carboxylic acid and its derivatives with diaryl diselenether and its derivatives.
Disclosure of Invention
The invention aims to provide a synthesis method of a 1, 1-diselenide olefin compound, which is used for generating a target product through the reaction of an alkenyl thianthrene salt compound and a diselenide compound. The reaction operation is simple and easy to control, the post-treatment is convenient, and the synthesis method of the 1, 1-diseleno substrate of the alkyl olefin is supplemented.
The technical scheme of the invention is as follows:
a method for synthesizing a 1, 1-diseleno olefin compound, which comprises the following steps:
mixing an alkenyl thianthrene salt compound (1 a) and a diselenide compound (1 b) with alkali, adding a solvent under the protection of nitrogen, reacting for 5-6 hours at room temperature, and performing post-treatment to obtain a product 1, 1-diselenide olefin compound (1 c);
wherein, the mol ratio of the alkenyl thianthrene salt compound (1 a), the diselenide compound (1 b) and the alkali is 1.0-1.1: 1:2.0 to 3.0;
the base is selected from sodium hydroxide, potassium tert-butoxide, potassium carbonate, etc., preferably potassium hydroxide;
the solvent is selected from tetrahydrofuran, acetonitrile, dichloromethane, N-dimethylformamide, and the like, preferably dichloromethane; the volume mole ratio of the solvent to the diselenide compound (1 b) is 5-10: 1, mL/mmol;
the specific post-treatment method comprises the following steps: after the reaction is finished, directly concentrating the reaction solution, performing column chromatography, taking pure petroleum ether as an eluent, collecting eluent containing a target compound, evaporating a solvent and drying to obtain a 1, 1-diseleno olefin compound (1 c);
the reaction general formula is as follows:
in the formula (1 a), (1 b) or (1 c),
r is C 1-8 Alkyl or C 3-8 Cycloalkyl; the C is 1-8 Alkyl or C 3-8 Cycloalkyl is unsubstituted or substituted with one or more groups independently selected from aryl, alkenyl, hydroxy, halo, trifluoromethyl, acyloxy, dialkylamino, sulfonyl, alkyl, or cycloalkyl; preferably R is cyclohexyl, octyl, bromopropyl, hydroxypropyl or phenethyl;
R 1 is C 1-8 Alkyl, C 3-8 Cycloalkyl, C 2-7 Heterocycloalkyl, aryl, heteroaryl, alkenyl, alkynyl or acyl; wherein the C 1-8 Alkyl, C 3-8 Cycloalkyl, C 2-7 Heterocycloalkyl, aryl, heteroaryl are unsubstituted or substituted with one or more groups independently selected from halogen, hydroxy, oxo, trifluoromethyl, aryl, alkyl, cycloalkyl, alkoxy, alkylamino, amido, aminoacyl, ester, acyloxy, or sulfonyl; preferably R 1 Is methyl, phenyl, p-methoxyphenyl, p-trifluoromethylphenyl, p-fluorophenyl, p-bromophenyl, p-methylphenyl or thienyl.
The synthesized 1, 1-diseleno olefin compound can react with butyl lithium reagent to obtain two useful organic synthesized building blocks, namely diseleno olefin and diseleno ether products respectively. The synthesized monoseleno-olefine product may be further converted into olefine compound. (Tetrahedron Lett.1982,23, 3411-3414)
The invention has the following advantages:
the reaction system is simple and easy to operate, the raw material preparation is simple, and the post-treatment is convenient. The innovation point of the invention is that the synthesis method of the 1, 1-diseleno olefin which is supplemented with alkyl olefin is provided. The method adopts no metal catalysis, and the raw material preparation is simple. The 1, 1-diseleno olefin prepared by the method can obtain medium and above yield.
Detailed Description
The present invention will be further illustrated by the following examples, but the scope of the present invention is not limited thereto.
In the following examples, diphenyl diselenide and dimethyl diselenide were purchased from An Naiji chemistry, diphenyl diselenide purity: 96%, purity of dimethyl diselenide: 97%; the remaining diselenide references: org. Lett.2010,12,15,3288-3291; all alkenyl thianthrene salts reference: angew.chem.int.ed.2020,59, 5616-5620.
Example 1
Synthesis of 2-cyclohexyl-1, 1-diphenyl selenoethylene
Cyclohexylalkenylthianthrene salt (84.7 mg,0.22 mmol), diphenyldiselenide (62.4 mg,0.2 mmol), potassium hydroxide (28.1 mg,0.5 mmol) was added to a 5mL microwave tube equipped with a magnetic stirrer to displace N 2 Three times, 1mL DCM was added and the reaction was allowed to proceed for 6h. Concentrating, subjecting to silica gel column chromatography, eluting with pure petroleum ether, concentrating to obtain 69.7mg of product with yield of 83%, and collecting colorless liquid. 1 H NMR(400MHz,CDCl 3 )δ7.43(m,4H),7.28(m,2.1Hz,6H),6.32(d,J＝9.2Hz,1H),2.66(m,1H),1.78–1.61(m,5H),1.38–1.24(m,2H),1.17(m,3H)ppm；13C NMR(101MHz,CDCl 3 )δ151.64,133.27(2C),132.67(2C),131.40,131.19,129.05(2C),128.90(2C),127.50,127.17,116.86,42.74,32.41(2C),25.84,25.56(2C)ppm；HRMS m/z(ESI)calcd for C 20 H 22 KSe 2 [M+K] + 460.9684,found:460.9679.
The structural formula of the product is as follows:
example 2
Synthesis of 1, 1-diphenylseleno-1-decene
Octyl alkenylthianthrene salt (97.2 mg,0.22 mmol), diphenyl diselenide (62.4 mg,0.2 mmol), potassium hydroxide (28.1 mg,0.5 mmol) were added to a 5mL microwave tube equipped with a magnetic stirrer to displace N 2 Three times, 1mL DCM was added and the reaction was allowed to proceed for 6h. Concentrating, subjecting to silica gel column chromatography, eluting with pure petroleum ether, concentrating to obtain 67.5mg of product with 75% yield, and collecting colorless liquid. 1 H NMR(400MHz,CDCl 3 )δ7.49–7.44(m,2H),7.44–7.38(m,2H),7.33–7.22(m,6H),6.44(t,J＝7.2Hz,1H),2.36(q,J＝7.3Hz,2H),1.47–1.36(m,2H),1.29(m,10H),0.91(t,J＝6.9Hz,3H)ppm； 13 CNMR(101MHz,CDCl 3 )δ145.86,133.64(2C),132.51(2C),131.24,131.14,129.07(2C),128.90(2C),127.63,127.12,118.66,33.65,31.85,29.70,29.37,29.24,29.18,28.91,22.67,14.10ppm；HRMS m/z(ESI)calcd for C 22 H 29 Se 2 [M+H] + 453.0594,found:453.0586.
The structural formula of the product is as follows:
example 3
Synthesis of 5-bromo-1, 1-diphenylseleno-1-butene
The procedure described in example 1 was followed except that the alkenylthianthrene salt substrate used was bromopropylthioanthracene salt (99.2 mg,0.22 mmol) to give 43.2mg of product in 47% yield as a colorless liquid. 1 H NMR(400MHz,CDCl 3 )δ7.51–7.46(m,2H),7.46–7.41(m,2H),7.36–7.24(m,6H),6.39–6.24(t,J＝7.2Hz,1H),3.38(t,J＝6.8Hz,2H),2.52(q,J＝7.3Hz,2H),2.05–1.87(m,2H)ppm；13C NMR(101MHz,CDCl 3 )δ141.55,134.15(2C),132.65(2C),130.76,130.72,129.25(2C),129.05(2C),128.03,127.40,121.22,32.78,32.21,31.94ppm；HRMS m/z(ESI)calcd for C 17 H 18 BrSe 2 [M+H] + 460.8917,found:460.8912.
The structural formula of the product is as follows:
example 4
Synthesis of 5, 5-diphenylseleno-4-alkenyl-1-pentanol
The procedure described in example 1 was followed except that the alkenylthianthrene salt used was hydroxypropylalkenylthianthrene salt (85.4 mg,0.22 mmol) to give 53.9mg of product in 68% yield as a colorless liquid. 1 H NMR(400MHz,DMSO-d6)δ7.45–7.40(m,2H),7.39–7.27(m,8H),6.49(t,J＝7.3Hz,1H),4.46(t,J＝5.1Hz,1H),3.37(q,J＝6.5,5.1Hz,2H),2.35(q,J＝7.4Hz,2H),1.59–1.45(m,2H)ppm；13C NMR(101MHz,DMSO-d6)δ147.27,133.27(2C),131.89(2C),131.10,131.08,129.95(2C),129.77(2C),128.30,127.66,117.66,60.60,32.17,30.63ppm；HRMS m/z(ESI)calcd for C 17 H 19 OSe 2 [M+H] + 398.9761,found:398.9757.
The structural formula of the product is as follows:
example 5
Synthesis of 4-phenyl-1, 1-diphenylseleno-1-butene
Ethylbenzene alkenylthianthrene salt (95.5 mg,0.22 mmol), diphenyldiselenide (-62.4 mg,0.2 mg), potassium hydroxide (28.1 mg,0.5 mmol) was added to a 5mL microwave tube equipped with a magnetic stirrer to displace N 2 Three times, 1mL DCM was added and the reaction was allowed to proceed for 6h. Concentrating, subjecting to silica gel column chromatography, eluting with pure petroleum ether, concentrating to obtain 62.8mg of product with 71% yield, and collecting colorless liquid.
1 H NMR(400MHz,DMSO-d6)δ7.33(m,5H),7.25(M,8H),7.15–7.09(m,2H),6.41(t,J＝6.8Hz,1H),2.77–2.56(m,4H). 13 C NMR(101MHz,DMSO-d6)δ145.9,141.2,133.5(2C),131.8(2C),131.1,130.8,129.9(2C),129.7(2C),129.0(2C),128.8(2C),128.4,127.6,126.4,118.6,35.5,34.6.HRMS m/z(ESI)calcd for C 20 H 20 KSe 2 [M+K] + 482.9527,found:482.9531
The structural formula of the product is as follows:
example 6
Synthesis of 4-phenyl-1, 1-bis (p-fluorophenyl) -1-butene
The procedure described in example 5 was followed except that the diselenide substrate used was p-fluorodiphenyl diselenide (69.6 mg,0.2 mmol) to give 71.7mg of the product in 75% yield as a colorless liquid. 1 H NMR(400MHz,DMSO-d6)δ7.35–7.25(m,4H),7.25–7.19(m,3H),7.18–7.05(m,6H),6.34(t,J＝6.9Hz,1H),2.69(m,2H),2.66–2.59(m,2H)ppm； 13 C NMR(101MHz,DMSO-d6)δ163.59(d,J＝28.3Hz),161.15(d,J＝27.6Hz),144.95,141.14,136.10(d,J＝8.1Hz)(2C),134.91(d,J＝8.0Hz)(2C),129.00(2C),128.77(2C),126.46,125.67(d,J C-F ＝3.6Hz),125.61(d,J C-F ＝3.3Hz),119.61,116.96(d,J C-F ＝21.6Hz,2C),116.71(d,J C-F ＝21.6Hz,2C),35.38,34.61ppm；HRMS m/z(ESI)calcd for C 22 H 19 F 2 Se 2 [M+H] + 480.9780,found:480.9795.
The structural formula of the product is as follows:
example 7
Synthesis of 4-phenyl 1, 1-bis (p-bromophenyl) -1-butene
The procedure described in example 5 was followed except that the diselenide substrate used was p-bromodiphenyl diselenide (93.9 mg,0.2 mmol) to give 80.0mg of the product in 60% yield as a colorless liquid. 1 H NMR(400MHz,DMSO-d6)δ7.39–7.11(m,14H),6.50(t,J＝7.0Hz,1H),2.72(m,2H),2.69–2.60(m,2H)ppm； 13 C NMR(101MHz,DMSO-d6)δ147.59,141.09,134.88(2C),133.89(2C),133.25,132.74,129.88,129.79(2C),129.62,129.58(2C),129.02(2C),128.80(2C),126.48,118.25,35.59,34.51ppm；HRMS m/z(EI)calcd for C 22 H 18 Br 2 Se 2 [M] + 599.8106,found:599.8101.
The structural formula of the product is as follows:
example 8
Synthesis of 4-phenyl-2, 2-bis (p-methoxyphenylseleno) -1-butene
The procedure described in example 5 was followed except that p-methoxydiphenyl diselenide (74.4 mg,0.2 mmol) was used as the diselenide substrate, to give 53.2mg of the product in 53% yield as a pale yellow liquid. 1 H NMR(400MHz,DMSO-d6)δ7.31–7.19(m,7H),7.10(dd,J＝6.9,1.7Hz,2H),6.94–6.84(m,4H),6.04(t,J＝6.7Hz,1H),3.78(s,3H),3.75(s,3H),2.66–2.54(m,4H)ppm； 13 C NMR(101MHz,DMSO-d6)δ160.00,159.59,141.27,140.23,136.62(2C),134.96(2C),128.96(2C),128.72(2C),126.37,121.34,120.37,120.30,115.64(2C),115.38(2C),55.68,55.65,35.07,34.83ppm；HRMS m/z(ESI)calcd for C 24 H 24 O 2 Se 2 [M] + 504.0107,found:504.0092.
The structural formula of the product is as follows:
example 9
Synthesis of 4-phenyl-2, 2-bis (p-trifluoromethylphenseleno) -1-butene
The procedure described in example 5 was followed except that p-trifluoromethyl diphenyl diselenide (89.6 mg,0.2 mmol) was used as the diselenide substrate to give 60.1mg of a product in 52% yield as a pale yellow liquid. 1 H NMR(400MHz,DMSO-d6)δ7.56(dd,J＝14.9,8.1Hz,4H),7.40(dd,J＝18.1,8.1Hz,4H),7.34–7.27(m,2H),7.27–7.16(m,3H),6.81(t,J＝7.0Hz,1H),2.80(m,2H),2.76–2.66(m,2H)ppm； 13 C NMR(101MHz,DMSO-d6)δ152.47,141.06,137.15(2C),136.94(2C),132.36(2C),131.90(2C),129.05(2C),128.94(2C),128.14(d,J C-F ＝31.7Hz,1C),127.89(d,J C-F ＝31.9Hz,1C),126.53,126.25(d,J C-F ＝3.9Hz,2C),124.80(d,J C-F ＝272.3Hz,2C),115.79,36.91,34.30ppm；HRMS m/z(EI)calcd for C 24 H 18 F 6 Se 2 [M] + 579.9643,found:579.9617.
The structural formula of the product is as follows:
example 10
Synthesis of 4-phenyl-2, 2-di (2-thiophene) seleno-1-butene
The procedure described in example 5 was followed except that the diselenide substrate used was bis (2-thienyl) diselenide (64.8 mg,0.20 mmol) to give 75.4mg of the product in 83% yield as a colorless liquid. 1 H NMR(400MHz,DMSO-d6)δ7.78(dd,J＝5.3,1.2Hz,1H),7.73(dd,J＝5.3,1.2Hz,1H),7.28–7.15(m,5H),7.14–7.09(m,3H),7.06(dd,J＝5.3,3.5Hz,1H),6.03–5.96(m,1H),2.65–2.55(m,4H)ppm； 13 C NMR(101MHz,DMSO-d6)δ141.12,139.24,137.67,136.93,133.88,133.09,129.18,128.92(2C),128.77(3C),126.40,123.72,123.06,122.52,34.91,34.71ppm；HRMS m/z(EI)calcd for C 18 H 16 S 2 Se 2 [M] + 455.9024,found:455.9004.
The structural formula of the product is as follows:
example 11
Synthesis of 4-phenyl-1, 1-dimethylseleno-1-butene
The procedure described in example 5 was followed, except that the diselenide substrate used was dimethyl diselenide (37.6 mg,0.20 mmol) to give40.7mg of product was obtained in 64% yield as colorless liquid. 1 H NMR(400MHz,DMSO-d6)δ7.31–7.25(m,2H),7.22–7.16(m,3H),6.11(t,J＝7.0Hz,1H),2.68(m,2H),2.56(m,2H),2.12(s,3H),2.08(s,3H)ppm； 13 CNMR(101MHz,DMSO-d6)δ141.60,137.33,128.86(2C),128.72(2C),126.35,120.05,35.02,34.95,9.18,9.02ppm；HRMS m/z(EI)calcd for C 12 H 16 Se 2 [M] + 319.9582,found:319.9571.
The structural formula of the product is as follows:
application example 1 (taking the product obtained in example 5 as an example)
Synthesis of 4-phenyl-1-phenylselenobutene and diphenyldiselenether (2.5 a)
4-phenyl-1, 1-diphenylseleno-1-butene (88.4 mg,0.2 mmol) was added to a 25mL microwave tube equipped with a magnetic stirrer to displace N 2 Three times, 1mL of THF solvent was added. N-butyllithium (0.2 ml,1 mol/L) was added at-78deg.C, reacted at room temperature for 30min, quenched with water at-78deg.C, and reacted at room temperature for 30min. THF was dried, extracted with ethyl acetate and the organic phase was collected. Purifying with silica gel column using pure petroleum ether as eluent, concentrating to obtain the product. 4-phenyl-1-phenylselenobutene (2.4 a): 50.1mg, 87% yield, colorless liquid; diphenyl diselenide (2.5 a): 26.5mg, yield 85%, yellow solid. (reference: tetrahedron Lett.1982,23, 3411-3414)
2.4a: 1 H NMR(400MHz,DMSO-d6)δ7.33–7.18(m,10H),6.46(m,1H),6.09(m,1H),2.73(t,J＝7.5Hz,2H),2.50–2.42(m,2H). 13 C NMR(101MHz,DMSO-d6)δ141.6,140.0,131.1,131.0(2C),129.9(2C),128.9(2C),128.7(2C),127.1,126.3,116.8,35.7,34.8.HRMS m/z(ESI)calcd for C 16 H 16 NaSe 2 [M+Na] + 311.0309,found:311.0300.
Application example 2
Synthesis of 4-phenyl-1-butene (2.4 c)
4-phenyl-1, 1-diphenylseleno-1-butene (88.4 mg,0.2 mmol) was added to a 25mL microwave tube equipped with a magnetic stirrer to displace N 2 Three times, 1mL of THF solvent was added. N-butyllithium (0.2 ml,1 mol/L) was added at-78deg.C, and reacted at room temperature for 30min, methyl iodide (28.4 mg,0.2 mmol) was added at-78deg.C, and reacted at room temperature for 30min. THF was dried, extracted with ethyl acetate and the organic phase was collected. Pure petroleum ether was used as eluent, purified by silica gel column and concentrated to give product 2.4b (48.2 mg, 80%). (reference: tetrahedron Lett.1982,23, 3411-3414)
2.4b: 1 H NMR(400MHz,DMSO-d6)δ7.33–7.26(m,7H),7.22(m,3H),5.91(m,1H),2.69(t,J＝7.4Hz,2H),2.46–2.38(m,2H),1.84(s,3H). 13 C NMR(101MHz,DMSO-d6)δ141.7,137.0,132.4(2C),130.2,129.8(2C),129.0(2C),128.7(2C),127.5,126.3,126.0,35.0 31.3,20.3.HRMS m/z(ESI)calcd for C 17 H 19 Se 2 [M+H] + 303.0646,found:303.0642.
2.4b (60 mg,0.2 mmol), tributyltin hydride (174.6 mg,0.6 mmol), azobisisobutyronitrile (3.3 mg,0.02 mmol) was added to a 5mL microwave tube equipped with a magnetic stirrer, 0.5mL benzene was added as solvent and reacted at 90℃for 3h. Pure petroleum ether is used as an eluent, and is purified by a silica gel column and concentrated to obtain 2.4c (13.2 mg, 45%), and the product is colorless transparent liquid. (ref: tetrahedron Lett.1982,23, 3411-3414).
Claims (6)
1. A method for synthesizing a 1, 1-diseleno olefin compound, which is characterized by comprising the following steps:
mixing an alkenyl thianthrene salt compound (1 a) and a diselenide compound (1 b) with alkali, adding a solvent under the protection of nitrogen, reacting for 5-6 hours at room temperature, and performing post-treatment to obtain a product 1, 1-diselenide olefin compound (1 c);
the reaction general formula is as follows:
in the formula (1 a), (1 b) or (1 c),
r is C 1-8 Alkyl or C 3-8 Cycloalkyl; the C is 1-8 Alkyl or C 3-8 Cycloalkyl is unsubstituted or substituted with one or more groups independently selected from aryl, alkenyl, hydroxy, halo, trifluoromethyl, acyloxy, dialkylamino, sulfonyl, alkyl, or cycloalkyl;
R 1 is C 1-8 Alkyl, C 3-8 Cycloalkyl, C 2-7 Heterocycloalkyl, aryl, heteroaryl, alkenyl, alkynyl or acyl; wherein the C 1-8 Alkyl, C 3-8 Cycloalkyl, C 2-7 Heterocycloalkyl, aryl, heteroaryl are unsubstituted or substituted with one or more groups independently selected from halogen, hydroxy, oxo, trifluoromethyl, aryl, alkyl, cycloalkyl, alkoxy, alkylamino, amido, aminoacyl, ester, acyloxy, or sulfonyl.
2. The method for synthesizing a 1, 1-diseleno olefin compound according to claim 1, wherein the molar ratio of the alkenylthianthrene salt compound (1 a), the diseleno ether compound (1 b), and the base is 1.0 to 1.1:1:2.0 to 3.0.
3. The method for synthesizing a 1, 1-diseleno olefin compound according to claim 1, wherein the base is selected from sodium hydroxide, potassium t-butoxide or potassium carbonate.
4. The method for synthesizing a 1, 1-diseleno olefin compound according to claim 1, wherein the solvent is selected from tetrahydrofuran, acetonitrile, methylene chloride, and N, N-dimethylformamide.
5. The method for synthesizing a 1, 1-diseleno olefin compound according to claim 1, wherein the volume molar ratio of the solvent to the diseleno ether compound (1 b) is 5 to 10:1, mL/mmol.
6. The method for synthesizing a 1, 1-diseleno olefin compound according to claim 1, wherein the post-treatment method comprises the steps of: after the reaction, the reaction solution was directly concentrated, column chromatography was performed using pure petroleum ether as an eluent, and the eluent containing the target compound was collected, and the solvent was distilled off and dried to obtain a 1, 1-diselenide compound (1 c).
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