CN104058908B - A kind of Olefination linked reaction method of naphthenic compounds - Google Patents
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006772 olefination reaction Methods 0.000 title claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 7
- 238000010189 synthetic method Methods 0.000 claims description 20
- 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
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 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
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 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
- 238000011160 research Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 150000001924 cycloalkanes Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- -1 styrene compound Chemical class 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method 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
- 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 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
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
The present invention relates to a kind of Olefination linked reaction method of naphthenic compounds, described method with cyclanes compound and styrene compound for raw material, at CuBr
2under the composite catalyst system of/TBHP/ auxiliary agent, achieve the direct Olefination linked reaction of cyclanes compound, and obtain the technique effect of high yield, the research having filled up cycloalkane substrate in prior art is blank, shows industrial applications prospect and important scientific research value very widely.
Description
Technical field
The present invention relates to a kind of Olefination linked reaction method of naphthenic compounds, relate more specifically to a kind of Olefination linked reaction method of naphthenic compounds of mantoquita/oxygenant/auxiliary agent composite catalyzing, belong to organic chemical industry and synthesize field.
Background technology
Nowadays, transition metal-catalyzed C-H ethylene linkageization reaction has caused the extensive concern of the field scientific research personnel such as organic, chemical industry, material gradually, and becomes a major challenge of synthetic chemistry in the last few years.This 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, FujiwaraYuzo etc. (" AromaticSubstitutionofOlefins.VI.ArylationofOlefinswithP alladium (II) Acetate ", J.Am.Chem.Soc., 1969,91,7166) alkene and the benzene derivative that have reported a kind of palladium chtalyst react the method preparing aryl-substituted olefins.Along with the progress in epoch, increasing catalysis synthesizing technology emerges in large numbers successively, illustratively as follows:
CaiGuixin etc. (" IndirectorthoFunctionalizationofSubstitutedToluenesthrou ghorthoOlefinationofN; N '-DimenthylbenzylaminesTunedbytheAcidityofReactionConditio ns ", J.Am.Chem.Soc., 2007,129,7666-7673) report a kind of replacement N, the Olefination reaction of the high regioselectivity of N-dimethyl benzylamine, it is regulated by the acidity in reaction conditions and is achieved, and its reaction formula is as follows:
MaartenD.K.Boele etc. (" SelectivePd-CatalyzedOxidativeCouplingofAnilideswithOlef insthroughC-HBondActivationatRoomTemperature ", J.Am.Chem.Soc., 2002, 124, 1586-1587) disclose a kind of selectivity good, the aryl olefinization reaction of oxidative coupling reaction gentleness, it adopts anils and acrylate to be raw material, reaction adopts electrophilic palladium complex to be catalyzer, under the oxygenant of cheapness exists, room temperature can be reacted, yield reaches as high as 91%, its reaction formula is as follows:
LiuChao etc. (" Nickel-CatalyzedHeck-TypeAlkenylationofSecondaryandTerti ary α-CarbonylAlkylBromides ", Angew.Chem.Int.Ed., 2012,51,3638-3641) report a kind of Heck type achieving secondary under nickel catalysis or three grades of alpha-carbonyl alkyl bromides and alkene first to react, its styrenic replaced and various 1,1-dialkyl group alkene all can be used as suitable reaction substrate, and its reaction formula is as follows:
Although relating to Olefination catalysis synthesizing technology in prior art has many, these methods or technique need further optimization, and the scope of application of such as reaction substrate still needs to be widened, and the direct Olefination 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 present 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 achieves the directly Olefination of alkane derivative, and reach the excellent effect of high yield, thus 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 present inventor, to this has been further investigation, after having paid a large amount of creative work, thus develops a kind of Olefination linked reaction method of naphthenic compounds, and then completes the present invention.
Specifically, 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, add formula (I) compound and formula (II) compound, then add and add CuBr successively
2with tertbutyl peroxide (TBHP), heat up under stirring and add auxiliary agent again, sealing thermal insulation reacts, mixture adds methylene dichloride after completion of the reaction, filter insolubles, finally concentrated by filter vacuum, resistates crosses 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, 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 non-limiting manner.
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 in the ratio of the auxiliary agent of gram (g) for 1:85-110, namely every mole (mol) described formula (I) compound uses 85-110 gram (g) described auxiliary agent, can be 1:85,1:90,1:95,1:100,1:105 or 1:110 in non-limiting manner.
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, such as, 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, such as 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 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 non-limiting manner.
In described synthetic method of the present invention, the reaction times is without particular limitation, such as, can be 8-10h, can be 8h, 8.5h, 9h, 9.5h or 10h in non-limiting manner.
In described synthetic method of the present invention, temperature of reaction is 80-100 DEG C, such as, can be 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C or 100 DEG C.
In described synthetic method of the present invention, silica gel column chromatography adopts sherwood oil as elutriant.In all embodiments 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, achieve the direct Olefination linked reaction of cycloalkyl compounds, and significantly improve reaction yield;
2, adopt specific copper catalyst/oxygenant/auxiliary combination and achieve unforeseeable excellent effect;
3, the impact of the actual conditions such as reagent type and temperature by lot of experiments.
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 any type of any restriction is formed to real protection scope of the present invention, 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 0.1mmolCuBr successively
2and 1mmolTBHP, the agent mixture of the BINAP that 95mg mass ratio is 1:5 and tributyl ammonium tosilate is added again under intensification stirring, seal 90 DEG C of insulation reaction 8.5h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, is finally concentrated by filter vacuum, resistates crosses silica gel chromatography, can obtain formula (III) compound, yield is 98.7%, and purity is 99.1% (HPLC).
1HNMR(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 0.15mmolCuBr successively
2and 1.8mmolTBHP, the agent mixture of the BINAP that 110mg mass ratio is 1:5 and tributyl ammonium tosilate is added again under intensification stirring, seal 80 DEG C of insulation reaction 10h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, is finally concentrated by filter vacuum, resistates crosses silica gel chromatography, can obtain formula (III) compound, yield is 99.1%, and purity is 98.8% (HPLC).
1HNMR(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 0.2mmolCuBr successively
2and 1.5mmolTBHP, the agent mixture of the BINAP that 100mg mass ratio is 1:5 and tributyl ammonium tosilate is added again under intensification stirring, seal 100 DEG C of insulation reaction 9h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, is finally concentrated by filter vacuum, resistates crosses silica gel chromatography, can obtain formula (III) compound, yield is 99.3%, and purity is 98.9% (HPLC).
1HNMR(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 0.1mmolCuBr successively
2and 2mmolTBHP, the agent mixture of the BINAP that 90mg mass ratio is 1:5 and tributyl ammonium tosilate is added again under intensification stirring, seal 85 DEG C of insulation reaction 10h, mixture adds methylene dichloride after completion of the reaction, filters insolubles, is finally concentrated by filter vacuum, resistates crosses silica gel chromatography, can obtain formula (III) compound, yield is 98.6%, and purity is 99.4% (HPLC).
1HNMR(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, implement embodiment 5-8 respectively in the mode identical with embodiment 1-4, 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
2be more suitable for the catalyzer as this reaction compound system compared with the palladium salt of other kind, other mantoquita all causes declining to a great extent of product yield as during catalyzer, which confirms mantoquita kind and is containing the crucial effect in adjuvant system, and have close effect between auxiliary agent.
Embodiment 9-12
Replace with except following kind except by oxygenant TBHP, implement embodiment 9-12 respectively in the mode identical with embodiment 1-4, the corresponding relation of component and experimental result is as shown in table 2 below.
Table 2
Embodiment 13-16
Replace with except following kind except by the BINAP in auxiliary agent, implement embodiment 13-16 respectively in the mode identical with embodiment 1-4, 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 do not added in auxiliary agent, implement embodiment 17-20 respectively in the mode identical with embodiment 1-4, the corresponding relation of component and experimental result is as shown in table 4 below.
Table 4
"--" expression is not added.
From the result of embodiment 1-4 and table 2-4, indivisible between each component that the present inventor finds whole system, wherein the conversion of oxygenant and adjuvant component kind or disappearance drastically influence the performance of catalyst system performance and direct relation product can the acquisition of high yield, wherein TBHP is the best oxygen agent of this system, BINAP and tributyl ammonium tosilate be best auxiliary combination, and their interaction makes the reaction impelled apparently in system between substrate.
Embodiment 21-24
Except change temperature of reaction, implement embodiment 21-24 respectively in the mode identical with embodiment 1-4, the corresponding relation of component and experimental result is as shown in table 5 below.
Table 5
From the result of embodiment 1-4 and table 5, the present inventor has investigated the impact of temperature of reaction on reaction process, the too low meeting of experiment proved response temperature causes sluggish carry out and can not fully react, temperature of reaction is too high may cause side reaction increase and reduce product yield, and therefore optimal temperature range is screened by experiment and drawn.
In sum; the present inventor is on the basis of literature research and a large amount of creative work; develop a kind of direct Olefination linked reaction of compound system catalysis naphthene-based compounds; compensate for the blank that prior art is studied cycloalkane substrate; and reach the technique effect of high yield; simultaneously to the optimization selection that the kind of all ingredients is carried out, there is mass-producing application prospect widely and scientific research value.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (8)
1. an Olefination linked reaction method for naphthenic compounds, described method comprises the steps: under atmosphere of inert gases, adds formula (I) compound and formula (II) compound, then add CuBr successively in reactor
2and tertbutyl peroxide, heat up under stirring and add auxiliary agent again, sealing thermal insulation reacts, mixture adds methylene dichloride after completion of the reaction, filters insolubles, is finally concentrated by filter vacuum, resistates crosses 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;
Described auxiliary agent is the mixture of BINAP and tributyl ammonium tosilate, and in described auxiliary agent, the mass ratio of BINAP and tributyl ammonium tosilate is 1:4.5-5.5.
2. synthetic method as claimed in claim 1, is characterized in that: in described auxiliary agent, the mass ratio of BINAP and tributyl ammonium tosilate is 1:5.
3. synthetic method as claimed in claim 1 or 2, is characterized in that: in mole described formula (I) compound with in gram the ratio of auxiliary agent for 1:85-110.
4. synthetic method as claimed in claim 1 or 2, is characterized in that: the mol ratio of described formula (I) compound and formula (II) compound is 1:3.5-5.5.
5. synthetic method as claimed in claim 1 or 2, is characterized in that: described formula (I) compound and CuBr
2mol ratio be 1:0.05-0.2.
6. synthetic method as claimed in claim 1 or 2, is characterized in that: the mol ratio 1:1-2 of described formula (I) compound and tertbutyl peroxide.
7. synthetic method as claimed in claim 1 or 2, is characterized in that: the reaction times is 8-10h.
8. synthetic method as claimed in claim 1 or 2, is characterized in that: temperature of reaction is 80-100 DEG C.
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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 |
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| Title |
|---|
| Nickel-Catalyzed Heck-Type Alkenylation of Secondary and Tertiary;Chao Liu, et al;《Angew. Chem. Int. Ed.》;20120301;第51卷;第3638-3641页 * |
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