CN104058908A - Olefin typed coupling reaction method for naphthene typed compounds - Google Patents
Olefin typed coupling reaction method for naphthene typed compounds Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 40
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 title abstract 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title abstract 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 238000010189 synthetic method Methods 0.000 claims description 22
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229950004288 tosilate Drugs 0.000 claims description 11
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 claims description 11
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 10
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- -1 isobutyl- Chemical group 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940051881 anilide analgesics and antipyretics Drugs 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
The invention relates to an olefin typed coupling reaction method for naphthene typed compounds. According to the method, naphthenic hydrocarbon compounds and styrene typed compounds serve as the raw materials, direct olefin typed coupling reaction of the naphthenic hydrocarbon compounds is achieved under a composite catalytic system of CuBr2/TBHP/addition agents, the high-yield technical effect is achieved, the research blank on the naphthenic hydrocarbon type substrate in the prior art is made up for, and the olefin typed coupling reaction method represents wide industrial application prospects and significant scientific research value.
Description
Technical field
The present invention relates to a kind of alkene linked reaction method of naphthenic compounds, relate more specifically to the alkene linked reaction method of the naphthenic compounds of a kind of mantoquita/oxygenant/auxiliary agent composite catalyzing, belong to the synthetic field of organic chemical industry.
Background technology
Nowadays, the field scientific research personnel's such as that the reaction of transition metal-catalyzed C-H ethylene linkageization has caused is gradually organic, chemical industry, material extensive concern, and become a major challenge of synthetic chemistry in the last few years.This is c h bond can be replaced by functionalized ethylene linkage based on this reaction, meets the requirement of atom economy.
As far back as the sixties in 20th century, Fujiwara Yuzo etc. (" Aromatic Substitution ofOlefins.VI.Arylation of Olefins with Palladium (II) Acetate ", J.Am.Chem.Soc., 1969,91,7166) a kind of alkene of palladium catalysis and the method that aryl substituted olefine is prepared in benzene derivative reaction have been reported.Along with the progress in epoch, increasing catalysis synthesizing technology emerges in large numbers successively, as follows as exemplifying:
Cai Guixin etc. (" Indirect ortho Functionalization of SubstitutedToluenes through ortho Olefination of N; N '-DimenthylbenzylaminesTuned by the Acidity of Reaction Conditions ", J.Am.Chem.Soc., 2007,129,7666-7673) reported a kind of replacement N, the alkene alkylation reaction of the high regioselectivity of N-dimethyl benzylamine, it is regulated and is achieved by the acidity in reaction conditions, and its reaction formula is as follows:
Maarten D.K.Boele etc. (" Selective Pd-Catalyzed OxidativeCoupling of Anilides with Olefins through C-H Bond Activation atRoom Temperature ", J.Am.Chem.Soc., 2002, 124, it is good 1586-1587) a kind of selectivity to be disclosed, the aryl olefinization reaction of oxidative coupling reaction gentleness, it adopts anils and acrylate is raw material, it is catalyzer that reaction adopts electrophilic palladium complex, under cheap oxygenant exists, room temperature can be reacted, yield reaches as high as 91%, its reaction formula is as follows:
Liu Chao etc. (" Nickel-Catalyzed Heck-Type Alkenylation ofSecondary and Tertiary α-Carbonyl Alkyl Bromides ", Angew.Chem.Int.Ed., 2012,51,3638-3641) reported that a kind of secondary or three grades of alpha-carbonyl alkyl bromides of having realized first under nickel catalysis react with the Heck type of alkene, the styrenic of its replacement and various 1,1-dialkyl group alkene all can be used as suitable reaction substrate, and its reaction formula is as follows:
Although it is existing many to relate to the catalysis synthesizing technology of alkene in prior art, these methods or technique need further optimization, and for example the scope of application of reaction substrate still needs to be widened, and the direct alkene alkylation reaction of simple alkane has no report; In addition, the condition of existing technique is to be improved, and reaction yield still needs to improve, etc.In view of this, the inventor is by the large quantity research to document, and the contrived experiment of science and developed a kind of novel catalyzed alkene reaction process, it has realized the direct alkene of alkane derivative, and reached the excellent effect of high yield, thereby there is very important using value and significance of scientific research.
Summary of the invention
In order to overcome above-mentioned pointed many defects, the inventor conducts in-depth research this, after having paid a large amount of creative works, thereby develops a kind of alkene linked reaction method of naphthenic compounds, and then has completed the present invention.
Particularly, technical scheme of the present invention and content relate to the synthetic method of a kind of formula (III) compound, described method comprises the steps: under atmosphere of inert gases, in reactor, adds formula (I) compound and formula (II) compound, then adds and adds successively CuBr
2and tertbutyl peroxide (TBHP), under the stirring that heats up, add again auxiliary agent, sealing thermal insulation reaction, mixture adds methylene dichloride after completion of the reaction, filters insolubles, finally by filtrate vacuum concentration, resistates is crossed silica gel chromatography, can obtain formula (III) compound;
Wherein, R
1for H, C
1-C
6alkyl or halogen;
N is the integer of 1-6.
In described synthetic method of the present invention, described halogen is fluorine, chlorine, bromine or iodine atom.
In described synthetic method of the present invention, described C
1-C
6alkyl refers to the alkyl with 1-6 carbon atom, and it can be straight or branched, and indefiniteness ground is such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl etc.
In described synthetic method of the present invention, n can be 1,2,3,4,5 or 6.
In described synthetic method of the present invention, described auxiliary agent is (±)-2,2 '-bis--(diphenylphosphine)-1, the mixture of 1 '-dinaphthalene (BINAP) and tributyl ammonium tosilate, wherein the mass ratio of BINAP and tributyl ammonium tosilate is 1:4.5-5.5, is preferably 1:5.
In described synthetic method of the present invention, in described formula (I) compound of mole (mol) with take the ratio of gram auxiliary agent of (g) as 1:85-110, be that every mole of (mol) described formula (I) compound is used 85-110 gram of (g) described auxiliary agent, can be to indefiniteness 1:85,1:90,1:95,1:100,1:105 or 1:110.
In described synthetic method of the present invention, the mol ratio of described formula (I) compound and formula (II) compound is 1:3.5-5.5, for example, can be 1:3.5,1:4,1:4.5,1:4 or 1:5.5.
In described synthetic method of the present invention, described formula (I) compound and CuBr
2mol ratio be 1:0.05-0.2, for example can be 1:0.05,1:0.1,1:0.15 or 1:0.2.
In described synthetic method of the present invention, the mol ratio 1:1-2 of described formula (I) compound and TBHP, can be to indefiniteness 1:1,1:1.1,1:1.2,1:1.3,1:1.4,1:1.5,1:1.6,1:1.7,1:1.8,1:1.9 or 1:2.
In described synthetic method of the present invention, the reaction times is without particular limitation, for example, can be 8-10h, can be to indefiniteness 8h, 8.5h, 9h, 9.5h or 10h.
In described synthetic method of the present invention, temperature of reaction is 80-100 ℃, for example, can be 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃.
In described synthetic method of the present invention, silica gel column chromatography adopts sherwood oil as elutriant.In all embodiment below, all use sherwood oil as elutriant.
In described synthetic method of the present invention, rare gas element is any one in nitrogen or argon gas.
Compared with prior art, beneficial effect of the present invention is:
1, realize the direct alkene linked reaction of cycloalkyl compounds, and significantly improved reaction yield;
2, adopt specific copper catalyst/oxygenant/auxiliary combination and obtained unforeseeable excellent effect;
3, by lot of experiments the impact of the actual conditionses such as reagent type and temperature.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not real protection scope of the present invention is formed to any type of any restriction, more non-protection scope of the present invention is confined to this.
Embodiment 1
Under nitrogen gas atmosphere, in reactor, add 1mmol formula (I) compound and 3.5mmol formula (II) compound, then add and add successively 0.1mmol CuBr
2and 1mmolTBHP, it is the agent mixture of BINAP and the tributyl ammonium tosilate of 1:5 that intensification adds 95mg mass ratio under stirring again, seal 90 ℃ of insulation reaction 8.5h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, finally by filtrate vacuum concentration, resistates is crossed silica gel chromatography, can obtain formula (III) compound, yield is 98.7%, and purity is 99.1% (HPLC).
1H NMR(500MHz,CDCl
3)δ7.31-7.28(m,4H),6.31(d,J＝16.0Hz,1H),6.16(dd,J＝16.0,6.9Hz,1H),2.17-2.10(m,1H),1.86-1.71(m,5H),1.38-1.15(m,5H)。
Embodiment 2
Under argon gas atmosphere, in reactor, add 1mmol formula (I) compound and 4.5mmol formula (II) compound, then add and add successively 0.15mmol CuBr
2and 1.8mmolTBHP, it is the agent mixture of BINAP and the tributyl ammonium tosilate of 1:5 that intensification adds 110mg mass ratio under stirring again, seal 80 ℃ of insulation reaction 10h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, finally by filtrate vacuum concentration, resistates is crossed silica gel chromatography, can obtain formula (III) compound, yield is 99.1%, and purity is 98.8% (HPLC).
1H NMR(500MHz,CDCl
3)δ7.44-7.42(m,1H),7.16-7.13(m,3H),6.52(d,J＝15.8Hz,1H),6.07(dd,J＝15.8,7.0Hz,1H),2.35(s,3H),2.18-2.17(m,1H),1.83-1.67(m,5H),1.34-1.21(m,5H)。
Embodiment 3
Under nitrogen gas atmosphere, in reactor, add 1mmol formula (I) compound and 5.5mmol formula (II) compound, then add and add successively 0.2mmol CuBr
2and 1.5mmolTBHP, it is the agent mixture of BINAP and the tributyl ammonium tosilate of 1:5 that intensification adds 100mg mass ratio under stirring again, seal 100 ℃ of insulation reaction 9h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, finally by filtrate vacuum concentration, resistates is crossed silica gel chromatography, can obtain formula (III) compound, yield is 99.3%, and purity is 98.9% (HPLC).
1H NMR(500MHz,CDCl
3)δ7.36-7.24(m,4H),7.18-7.15(m,1H),6.34(d,J＝15.8Hz,1H),6.21(dd,J＝15.8,7.8Hz,1H),2.64-2.59(m,1H),1.87-1.36(m,8H)。
Embodiment 4
Under argon gas atmosphere, in reactor, add 1mmol formula (I) compound and 5mmol formula (II) compound, then add and add successively 0.1mmol CuBr
2and 2mmolTBHP, it is the agent mixture of BINAP and the tributyl ammonium tosilate of 1:5 that intensification adds 90mg mass ratio under stirring again, seal 85 ℃ of insulation reaction 10h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, finally by filtrate vacuum concentration, resistates is crossed silica gel chromatography, can obtain formula (III) compound, yield is 98.6%, and purity is 99.4% (HPLC).
1H NMR(500MHz,CDCl
3)δ7.35-7.26(m,4H),7.19-7.16(m,1H),6.31(d,J＝15.9Hz,1H),6.23(dd,J＝15.9,7.5Hz,1H),2.35-2.33(m,1H),1.84-1.39(m,12H)。
Embodiment 5-8
Remove CuBr
2replace with outside following component, in the mode identical with embodiment 1-4, implemented respectively embodiment 5-8, the corresponding relation of component and experimental result is as shown in table 1 below.
Table 1
From the result of embodiment 1-4 and table 1, CuBr
2palladium salt compared with other kind is more suitable for the catalyzer as this reaction compound system, and other mantoquita all causes declining to a great extent of product yield during as catalyzer, and it has confirmed that mantoquita kind is in the key impact containing in adjuvant system, and between auxiliary agent, has close effect.
Embodiment 9-12
Except oxygenant TBHP is replaced with following kind, in the mode identical with embodiment 1-4, implemented respectively embodiment 9-12, the corresponding relation of component and experimental result is as shown in table 2 below.
Table 2
Embodiment 13-16
Except the BINAP in auxiliary agent is replaced with following kind, in the mode identical with embodiment 1-4, implemented respectively embodiment 13-16, the corresponding relation of component and experimental result is as shown in table 3 below.
Table 3
Embodiment 17-20
Except the component 2 tributyl ammonium tosilate that do not add in auxiliary agent, in the mode identical with embodiment 1-4, implemented respectively embodiment 17-20, the corresponding relation of component and experimental result is as shown in table 4 below.
Table 4
"--" represents not add.
Result from embodiment 1-4 and table 2-4, the inventor finds that between each component of whole system be indivisible, wherein the conversion of oxygenant and adjuvant component kind or disappearance are having a strong impact on the performance of catalyst system performance and direct relation the acquisition that can product high yield, best oxygen agent, BINAP and tributyl ammonium tosilate that wherein TBHP is this system are best auxiliary combination, and their interaction makes to have impelled apparently the reaction between substrate in system.
Embodiment 21-24
Except changing temperature of reaction, in the mode identical with embodiment 1-4, implemented respectively embodiment 21-24, the corresponding relation of component and experimental result is as shown in table 5 below.
Table 5
Result from embodiment 1-4 and table 5, the inventor has investigated the impact of temperature of reaction on reaction process, experimental results show that the too low meeting of temperature of reaction causes sluggish carry out and can not fully react, temperature of reaction is too high may be caused side reaction to increase and reduce product yield, and therefore optimal temperature range is screened and drawn by experiment.
In sum; the inventor is on the basis of literature research and a large amount of creative works; developed a kind of direct alkene linked reaction of compound system catalysis cycloalkane compound; made up the blank of prior art to the research of cycloalkane substrate; and reached the technique effect of high yield; the optimization selection of simultaneously kind of all ingredients being carried out, has mass-producing application prospect widely and scientific research and is worth.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. an alkene linked reaction method for naphthenic compounds, described method comprises the steps: under atmosphere of inert gases, in reactor, adds formula (I) compound and formula (II) compound, then adds and adds successively CuBr
2and tertbutyl peroxide (TBHP), under the stirring that heats up, add again auxiliary agent, sealing thermal insulation reaction, mixture adds methylene dichloride after completion of the reaction, filters insolubles, finally by filtrate vacuum concentration, resistates is crossed silica gel chromatography, can obtain formula (III) compound;
Wherein, R
1for H, C
1-C
6alkyl or halogen;
N is the integer of 1-6.
2. synthetic method as claimed in claim 1, is characterized in that: described auxiliary agent is the mixture of BINAP and tributyl ammonium tosilate.
3. the synthetic method as described in claim 1-2 any one, is characterized in that: in described auxiliary agent, the mass ratio of BINAP and tributyl ammonium tosilate is 1:4.5-5.5.
4. the synthetic method as described in claim 1-3 any one, is characterized in that: in described auxiliary agent, the mass ratio of BINAP and tributyl ammonium tosilate is 1:5.
5. the synthetic method as described in claim 1-4 any one, is characterized in that: in described formula (I) compound of mole (mol) with take the ratio of gram auxiliary agent of (g) as 1:85-110.
6. the synthetic method as described in claim 1-5 any one, is characterized in that: the mol ratio of described formula (I) compound and formula (II) compound is 1:3.5-5.5.
7. the synthetic method as described in claim 1-6 any one, is characterized in that: described formula (I) compound and CuBr
2mol ratio be 1:0.05-0.2.
8. the synthetic method as described in claim 1-7 any one, is characterized in that: the mol ratio 1:1-2 of described formula (I) compound and TBHP.
9. the synthetic method as described in claim 1-8 any one, is characterized in that: the reaction times is 8-10h.
10. the synthetic method as described in claim 1-9 any one, is characterized in that: temperature of reaction is 80-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410313429.6A CN104058908B (en) | 2014-07-02 | 2014-07-02 | A kind of Olefination linked reaction method of naphthenic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410313429.6A CN104058908B (en) | 2014-07-02 | 2014-07-02 | A kind of Olefination linked reaction method of naphthenic compounds |
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| Publication Number | Publication Date |
|---|---|
| CN104058908A true CN104058908A (en) | 2014-09-24 |
| CN104058908B CN104058908B (en) | 2015-12-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102153592A (en) * | 2010-11-22 | 2011-08-17 | 温州大学 | Suzuki-Miyaura coupling reaction of catalyzing aryl chloride by N-heterocyclic carbine-palladium-imidazole complex at room temperature under condition of water phase |
| CN102942429A (en) * | 2012-11-26 | 2013-02-27 | 大连理工大学 | Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153592A (en) * | 2010-11-22 | 2011-08-17 | 温州大学 | Suzuki-Miyaura coupling reaction of catalyzing aryl chloride by N-heterocyclic carbine-palladium-imidazole complex at room temperature under condition of water phase |
| CN102942429A (en) * | 2012-11-26 | 2013-02-27 | 大连理工大学 | Method for preparing aza or thia aryl biaryl compound by aid of palladium and carbon catalysts |
Non-Patent Citations (1)
| Title |
|---|
| CHAO LIU, ET AL: "Nickel-Catalyzed Heck-Type Alkenylation of Secondary and Tertiary", 《ANGEW. CHEM. INT. ED.》, vol. 51, 1 March 2012 (2012-03-01), pages 3638 - 3641 * |
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