CN111303194B - Synthesis method of B (4,5) alkenyl substituted carborane derivative - Google Patents
Synthesis method of B (4,5) alkenyl substituted carborane derivative Download PDFInfo
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- CN111303194B CN111303194B CN202010266279.3A CN202010266279A CN111303194B CN 111303194 B CN111303194 B CN 111303194B CN 202010266279 A CN202010266279 A CN 202010266279A CN 111303194 B CN111303194 B CN 111303194B
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- 125000003342 alkenyl group Chemical group 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 150000002576 ketones Chemical class 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 150000001408 amides Chemical class 0.000 claims abstract description 8
- 238000006880 cross-coupling reaction Methods 0.000 claims abstract description 4
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical group [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 11
- 229940071536 silver acetate Drugs 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- -1 1-carboxyl-2-n-butyl o-carborane Chemical compound 0.000 claims description 7
- KLTVSWGXIAYTHO-UHFFFAOYSA-N 1-Octen-3-one Chemical compound CCCCCC(=O)C=C KLTVSWGXIAYTHO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical group [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- QVLTVILSYOWFRM-UHFFFAOYSA-L CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C Chemical class CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C QVLTVILSYOWFRM-UHFFFAOYSA-L 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003283 rhodium Chemical class 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000003380 propellant Substances 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 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
- 241000271042 Gloydius halys Species 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000126 substance Substances 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
- C07F5/027—Organoboranes and organoborohydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method of a B (4,5) alkenyl substituted carborane derivative, which takes 1-carboxyl-2- (substituted) o-carborane and alpha, beta unsaturated ester, ketone and amide alkenyl reagents as raw materials, and generates decarboxylation cross-coupling reaction in a solvent in the presence of a catalyst and an additive to generate the B (4,5) alkenyl substituted o-carborane. The reactants involved in the invention have good universality, and the functional groups of the substrate have good compatibility; the alpha, beta unsaturated ester, ketone and amide which are simple and easy to obtain are used as the alkenyl reagent, so that the relative cost is low; the related reaction selectivity and yield are high, the reaction system is single in composition, the post-treatment is simple, and the implementation is easy.
Description
Technical Field
The invention belongs to the technical field of carborane synthesis, and particularly relates to a synthesis method of a B (4,5) alkenyl substituted carborane derivative.
Background
The carborane is a polyhedral closed cage-shaped structure, has the characteristics of high heat value, high boron content, good thermal stability and chemical stability and the like, and is a high-burning-rate catalyst with excellent performance. In addition, carboranes are used as metal ligands and neutron absorbing materials in the fields of coordination chemistry and medicine; the compounds are liquid at normal temperature, and have the functions of a plasticizer in the solid propellant besides the function of mainly regulating the burning rate.
Currently, the carborane burning rate catalysts commonly used include n-butyl carborane, n-hexyl carborane (NHC), carboranyl methylpropionate and the like. Much research is done on NHC, which has a heat of combustion of 56 MJ/kg. NHC is used for external use to develop a series of high burning rate propellants, wherein the addition amount of a catalyst is 10-14%, for example, NHC with the addition mass fraction of 13.1% is used as a burning rate catalyst in a hydroxyl propellant of an anti-tank missile of Agkistrodon halys, the formula burning rate is 144mm/s, and the pressure index is 0.65(13.8 MPa). 1-n-hexyl-1, 2-carborane has become a carborane burning rate regulator variety which is produced and applied in large scale due to the excellent comprehensive performance in the high burning rate propellant formula. For carborane derivatives functionalized on butylated hydroxyl propellants, the current modification is mainly focused on carbon atoms, and due to the problems of selectivity and the need to introduce specific functional groups to ensure high combustion heat values, few reports are made on the application of modification on boron atoms. However, due to the advantages of the number of boron, the modification possibility is increased, and the advantages of the sterically-polysubstituted active group, such as small influence on the overall performance, and the like, the introduction of the functionalized group on the boron atom provides better application prospects for the use of the functionalized group in the hydroxyl propellant.
Disclosure of Invention
Technical problem to be solved
The invention provides a synthesis method of a B (4,5) alkenyl substituted carborane derivative, which aims to solve the technical problem of how to synthesize the B (4,5) alkenyl substituted carborane derivative with high selectivity, high yield and good reactant universality.
(II) technical scheme
In order to solve the technical problems, the invention provides a synthesis method of a B (4,5) alkenyl substituted carborane derivative, which takes 1-carboxyl-2- (substituted) o-carborane and alpha, beta unsaturated ester, ketone and amide alkenyl reagents as raw materials, and generates decarboxylation cross-coupling reaction in a solvent in the presence of a catalyst and an additive to generate the B (4,5) alkenyl substituted o-carborane;
the reaction equation of the synthesis method is as follows:
wherein R is 1 Is straight-chain alkyl, aryl or substituted aryl, R 2 Is an alkyl group, an aryl group, an ether group or an amino group.
Further, the 1-carboxy-2- (substituted) o-carborane is 1-carboxy-1, 2-o-carborane, 1-carboxy-2-methyl o-carborane, 1-carboxy-2-n-butyl o-carborane, 1-carboxy-2-n-hexyl o-carborane or 1-carboxy-2-substituted phenyl o-carborane;
further, the alpha, beta unsaturated ester, ketone and amide alkenyl reagent is methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, phenyl acrylate, benzyl acrylate, methyl vinyl ketone, 1-octen-3-one or 1-aryl-2-propenyl-1-one; wherein, the aryl is phenyl or substituted phenyl, the benzene ring contains one or more substituent groups, and the substituent group on the benzene ring is methyl, methoxy, halogen or trifluoromethyl.
Further, the catalyst is a monovalent rhodium salt or a divalent palladium salt.
Further, the catalyst is palladium acetate, palladium chloride, dichloroditriphenylphosphine palladium, palladium trifluoroacetate or dichloropentamethylcyclopentadienylrhodium dimer.
Further, the additive is a silver salt.
Further, the additive is silver acetate, silver carbonate, silver oxide or silver trifluoroacetate.
Further, the solvent is dioxane, toluene, o-xylene or 1, 2-dichloroethane.
Further, the molar ratio of the 1-carboxyl-2- (substituted) o-carborane to the catalyst is (1-50): 1; the molar ratio of the 1-carboxyl-2- (substituted) o-carborane to the additive is 1 (1-20); the molar ratio of the 1-carboxyl-2- (substituted) o-carborane to the alpha, beta unsaturated ester, ketone and amide alkenylation reagents is 1 (1-20).
Furthermore, the reaction temperature of the synthesis method is 50-100 ℃, and the reaction time is 12-36 h.
(III) advantageous effects
The invention provides a synthesis method of a B (4,5) alkenyl substituted carborane derivative, which takes 1-carboxyl-2- (substituted) o-carborane and alpha, beta unsaturated ester, ketone and amide alkenyl reagents as raw materials, and generates decarboxylation cross-coupling reaction in a solvent in the presence of a catalyst and an additive to generate the B (4,5) alkenyl substituted o-carborane.
Compared with the prior art, the invention has the following beneficial effects:
1. the reactant has good universality, and the functional group of the substrate has good compatibility;
2. the invention uses simple and easily obtained alpha, beta unsaturated ester, ketone and amide as the alkenyl reagent, and has relatively low cost;
3. the method has the advantages of high reaction selectivity and yield, single reaction system composition, simple post-treatment and easy implementation.
Detailed Description
In order to make the objects, contents and advantages of the present invention more apparent, the following detailed description of the present invention will be given in conjunction with examples.
Example 12 Synthesis of n-hexyl-4, 5-bis (methyl acrylate) -1, 2-carborane
A20 mL Schlenk tube is filled with magnetons, 55mg (0.2mmol) of 1-carboxyl-2-n-hexyl o-carborane, 4mg (0.02mmol) of palladium acetate, 133mg (0.8mmol) of silver acetate and 41mg (0.48mmol) of methyl acrylate are sequentially added, then 5mL of 1, 2-dichloroethane is added, the reaction is carried out on an electromagnetic heating stirrer for 18 hours at the temperature of 70 ℃, after the reaction is finished, the solvent is evaporated, and the 2-n-hexyl-4, 5-bis (methyl acrylate) -1, 2-carborane is obtained by column chromatography purification, wherein the yield is 70mg, and the yield is 88%.
And (3) structural identification:
1 h NMR (500MHz, deuterated chloroform, δ/ppm) δ δ 6.91(d, J ═ 17.8Hz,2H),6.21(d, J ═ 17.8Hz,2H),3.74(s,7H),2.26 to 2.17(m,2H),1.46 to 1.41(m,2H),1.30 to 1.23(m,6H),0.88(t, J ═ 6.9Hz,3H). 13 C NMR (126MHz, deuterated chloroform,. delta./ppm) delta 166.12,133.38,75.38,61.15,51.67,38.05,31.20,29.16,28.49,22.36,13.88. 11 B NMR (160MHz, deuterated chloroform, delta/ppm) delta-3.06 (1B), -5.69(3B), -8.56(2B), -11.85(2B), -12.93 (2B).
High resolution mass spectrometry: mass to charge ratio C 16 B 10 H 31 O 4 [M-H] - The theoretical value is as follows: 397.3158; measured value: 397.3161.
the above structural characterization data confirmed that the compound obtained was 2-n-hexyl-4, 5-bis (methyl acrylate-1, 2-carborane.
Examples 2 to 13
Examples 2 to 13 2-n-hexyl-4, 5-bis () methyl acrylate) -1, 2-carborane was synthesized according to the same method as in example 1, and the influence of the reaction conditions on the product yield was investigated by adjusting parameters such as additives, solvents and time, and the experimental results are shown in the following table:
| examples | Additive agent | Solvent(s) | Temperature of | Time | Yield of |
| 2 | Silver oxide (0.8mmol) | 1, 2-dichloroethane | 70℃ | 18h | 58％ |
| 3 | Silver carbonate (0.8mmol) | 1, 2-dichloroethane | 70℃ | 18h | 73％ |
| 4 | Silver trifluoroacetate (0.8mmol) | 1, 2-dichloroethane | 70℃ | 18h | 65％ |
| 5 | Silver acetate (0.8mmol) | 1, 2-dichloroethane | 70℃ | 18h | 88％ |
| 6 | Copper acetate (0.8mmol) | 1, 2-dichloroethane | 70℃ | 18h | 35％ |
| 7 | Silver acetate (0.8mmol) | N, N-dimethylformamide | 70℃ | 18h | <5％ |
| 8 | Silver acetate (0.8mmol) | 1, 4-dioxane | 70℃ | 18h | 25％ |
| 9 | Silver acetate (0.8mmol) | Toluene | 70℃ | 18h | 53％ |
| 10 | Silver acetate (0.8mmol) | 1, 2-dichloroethane | 60℃ | 18h | 33％ |
| 11 | Silver acetate (0.8mmol) | 1, 2-dichloroethane | 80℃ | 18h | 82％ |
| 12 | Silver acetate (0.8mmol) | 1, 2-dichloroethane | 100℃ | 18h | 77％ |
| 13 | Silver acetate (0.8mmol) | 1, 2-dichloroethane | 70℃ | 36h | 85％ |
Examples 14 to 27
Examples 14 to 27B (4,5) alkenyl-substituted carborane was synthesized in the same manner as in example 2, and the influence of the reaction conditions on the product yield was investigated by adjusting the type of α, β unsaturated ester, ketone, amide alkenylation reagent, and the experimental results are shown in the following table:
| examples | Alpha, beta unsaturated ester, ketone, amide alkenylation reagent | Yield of |
| 14 | Acrylic acid ethyl ester | 82 |
| 15 | Acrylic acid n-butyl ester | 80％ |
| 16 | (iv) acrylic acid tert-butyl ester | 85％ |
| 17 | Phenyl acrylate | 77％ |
| 18 | Benzyl acrylate | 80％ |
| 19 | Methyl vinyl ketone | 72％ |
| 20 | 1-octen-3-one | 65％ |
| 21 | 1-phenyl-2-propenyl-1-one | 57％ |
| 22 | 1- (4-methyl-phenyl) -2-propenyl-1-one | 42％ |
| 23 | 1- (3-methyl-phenyl) -2-propenyl-1-one | 43％ |
| 24 | 1- (2-methyl-phenyl) -2-propenyl-1-one | 55％ |
| 25 | 1- (4-methoxy-phenyl) -2-propenyl-1-one | 63％ |
| 26 | N, N-2-methyl acrylamide | 78％ |
| 27 | N-tert-butylacrylamide | 82％ |
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A synthesis method of a B (4,5) alkenyl substituted carborane derivative is characterized in that 1-carboxyl-2- (substituted) o-carborane and alpha, beta unsaturated ester, ketone and amide alkenylation reagents are used as raw materials, and decarboxylation cross-coupling reaction is carried out in a solvent in the presence of a catalyst and an additive to generate the B (4,5) alkenyl substituted o-carborane; wherein,
the 1-carboxyl-2- (substituted) o-carborane is 1-carboxyl-1, 2-o-carborane, 1-carboxyl-2-methyl o-carborane, 1-carboxyl-2-n-butyl o-carborane, 1-carboxyl-2-n-hexyl o-carborane or 1-carboxyl-2-substituted phenyl o-carborane;
the alpha, beta unsaturated ester, ketone and amide alkenylation reagent is methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, phenyl acrylate, benzyl acrylate, methyl vinyl ketone, 1-octen-3-one or 1-aryl-2-propenyl-1-one; wherein, the aryl is phenyl or substituted phenyl, the benzene ring contains one or more substituent groups, and the substituent group on the benzene ring is methyl, methoxy, halogen or trifluoromethyl;
the catalyst is monovalent rhodium salt or divalent palladium salt; the additive is silver salt; the solvent is dioxane, toluene, o-xylene or 1, 2-dichloroethane;
the reaction equation of the synthesis method is as follows:
wherein R is 1 Is a linear alkyl, aryl or substituted aryl radical, R 2 Is an alkyl group, an aryl group, an ether group or an amino group.
2. The method of synthesis of claim 1, wherein the catalyst is palladium acetate, palladium chloride, dichlorobistriphenylphosphine palladium, palladium trifluoroacetate, or dichloropentamethylcyclopentadienylrhodium dimer.
3. The method of synthesis of claim 1, wherein the additive is silver acetate, silver carbonate, silver oxide or silver trifluoroacetate.
4. The synthesis method of claim 1, wherein the molar ratio of the 1-carboxy-2- (substituted) o-carborane to the catalyst is (1-50: 1; the molar ratio of the 1-carboxyl-2- (substituted) o-carborane to the additive is 1 (1-20); the molar ratio of the 1-carboxyl-2- (substituted) o-carborane to the alpha, beta unsaturated ester, ketone and amide alkenylation reagents is 1 (1-20).
5. The synthesis method according to claim 1, wherein the reaction temperature of the synthesis method is 50-100 ℃ and the reaction time is 12-36 h.
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| CN202010266279.3A CN111303194B (en) | 2020-04-07 | 2020-04-07 | Synthesis method of B (4,5) alkenyl substituted carborane derivative |
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