CN107955031A - A kind of method that disilane class compound is continuously prepared using micro-reaction device - Google Patents
A kind of method that disilane class compound is continuously prepared using micro-reaction device Download PDFInfo
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- CN107955031A CN107955031A CN201711265557.8A CN201711265557A CN107955031A CN 107955031 A CN107955031 A CN 107955031A CN 201711265557 A CN201711265557 A CN 201711265557A CN 107955031 A CN107955031 A CN 107955031A
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- organosilan
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 21
- -1 disilane class compound Chemical class 0.000 title claims abstract description 11
- 229910000077 silane Inorganic materials 0.000 claims abstract description 27
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000011049 filling Methods 0.000 claims abstract description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 25
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 125000006182 dimethyl benzyl group Chemical group 0.000 claims description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- JTGAUXSVQKWNHO-UHFFFAOYSA-N ditert-butylsilicon Chemical compound CC(C)(C)[Si]C(C)(C)C JTGAUXSVQKWNHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 abstract description 12
- 238000005859 coupling reaction Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000010953 base metal Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 27
- 239000002585 base Substances 0.000 description 17
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000005784 autoimmunity Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 208000011580 syndromic disease Diseases 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000006621 Wurtz reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SKDKWDVYZOKBPL-UHFFFAOYSA-N benzyl(dimethyl)silicon Chemical compound C[Si](C)CC1=CC=CC=C1 SKDKWDVYZOKBPL-UHFFFAOYSA-N 0.000 description 1
- YXMVRBZGTJFMLH-UHFFFAOYSA-N butylsilane Chemical compound CCCC[SiH3] YXMVRBZGTJFMLH-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- QLSPZKGJDKBESW-UHFFFAOYSA-N cyclopenta-1,3-diene;iron Chemical compound [Fe].C1C=CC=C1 QLSPZKGJDKBESW-UHFFFAOYSA-N 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a kind of method that disilane class compound is continuously prepared using micro-reaction device, comprise the following steps：(1) solution A is dissolved in that the first organic solvent is prepared to obtain or solution A is organosilan by organosilan；(2) solution B is dissolved in that the second organic solvent is prepared to obtain or solution B is oxidant by oxidant；(3) solution A and solution B are pumped into the micro-mixer in micro-reaction device at the same time respectively and are mixed, carrying out reaction in the microreactor then flowed into micro-reaction device is prepared disilane class compound；Wherein, catalyst filling in the microreactor.The required raw material of the present invention is easy to get and stability is preferable, by the use of metallic copper class compound as catalyst, carries out coupling reaction to three substituted silanes, is better than base metal catalysts and transiting state metal catalyst to trisubstituted silane coupled effect；Micro passage reaction is because of its good mixing and heat transfer property, suitable for exothermic coupling reaction.
Description
Technical field
The invention belongs to chemical industry synthesis field, is related to compound preparation, and in particular to one kind is continuous using micro-reaction device
The method for preparing disilane class compound.
Background technology
Disilane is a kind of compound important in organosilan.Since last century the eighties, Miller, West,
Trefonas, Harrah, Kepler et al. find successively organodisilane have remarkable electronic property, photoelectric property and
Optical property.Patent CN2004100286490 and TW093101272 indicate work of the disilane on polysilicon germanium layer is formed
With illustrating great function of the disilane in semicon industry.Patent US20050245227 indicates the excellent light of disilane
Electrical effect, has a wide range of applications in the manufacture of optics electric appliance.Patent US19920857838 indicates the excellent light of disilane
Property is learned, has great function in the manufacture of film class optical device.It is excellent that patent US19830564293 then indicates disilane
Material property, can be used in combination with other multiple materials.
In conclusion due to the good photoelectricity of disilane, material property so that it is anti-that the synthesis of disilane becomes organosilan
An important ring in answering.Also, synthesis of the synthetic method of disilane to polysilane has huge reference.Traditional conjunction
Realized into method by Wurtz reactions.Wurtz coupling methods are by disubstituted dichlorosilane (or monosubstituted base trichlorine
Silane) it is placed in non-polar aromatic atent solvent, metallic sodium or potassium are added, carries out dechlorination condensation.Common solvent has first
Alkane of benzene, dimethylbenzene or higher etc..Dehalogenation is coupled to form disilane halogenated silanes in the presence of base, and this method is to list
Substituent trihalosilane and disubstituted dihalide halosilanes have good applicability, but three substituent halogenated silanes are fitted
It is poor with property.In addition, reaction requirement is necessary for the silane of halo, it is invalid to non-halogenated silane.Moreover, the reaction is also
There are it is many shortcomings that.To be attached to firstly, since there are oxygen atom in reaction process on alkali metal, ultimately form oxosilane and
The impurity of the oxosilane of poly.Secondly, halogenated silanes is not easy to maintain, and reaction environment friendly is poor.Moreover, the condition of this reaction
Relatively harsh, the input danger of metallic sodium is larger, and reaction process is difficult to control.
Tetsuo, Masato et al. subsequently have found that transiting state metal rhodium can be used for being catalyzed the autoimmunity syndrome of organosilan,
Hereafter, great development has been obtained using transiting state metal catalysis silane autoimmunity syndrome, it has been found that a variety of to be catalyzed silicon
The transiting state metal of alkane coupling, mainly including Zr, Hf, Ti, Mn, Rh, Ir, Pd, Pt, Sm.React, utilized compared to Wurtz
Crossing the silane coupled disilane that formed of state metal catalytic has huge progress.Organosilan can be directly as original in this kind of method
Material is coupled, without halogenated silanes as raw material.But coupling of these catalyst only to monosubstituted and disubstituted silane
Effect is preferable, poor to trisubstituted silane coupled effect.In addition, such catalyst is expensive, and the coupling reaction being catalyzed
More slowly, reaction condition is more harsh, and there is great limitation.
Hiroshi et al. has found that the compound of cyclopentadiene iron has catalytic effect to silane autoimmunity syndrome, reacts in purple
Under outer illumination, the three substituted silanes coupled products of itself can be effectively obtained.In addition, by adjusting reaction condition, this method
Can be with the higher polysilane of synthesized polymer degree.
The content of the invention
Goal of the invention：Poor for applicability, dangerous big to solve base metal catalysts in the prior art, transiting state metal is catalyzed
The problems such as agent is poor, expensive to trisubstituted silane coupling agent effect, the present invention provides one kind to utilize micro-reaction device system
The standby method for continuously preparing disilane class compound.
Technical solution：A kind of method that disilane class compound is continuously prepared using micro-reaction device of the present invention, bag
Include following steps：
(1) solution A is dissolved in that the first organic solvent is prepared to obtain or solution A is organosilan by organosilan；
(2) solution B is dissolved in that the second organic solvent is prepared to obtain or solution B is oxidant by oxidant；
(3) step (1) solution A and step (2) described solution B are pumped at the same time respectively micro- mixed in micro-reaction device
Mixed in clutch, carrying out reaction in the microreactor then flowed into micro-reaction device is prepared disilane class chemical combination
Thing；Wherein, catalyst filling in the microreactor.
Wherein, step (1) described organosilan is any one or a few in compound I；
R1R2R3SiH
I, wherein, R1、R2、R3It is each independently selected from aryl or alkyl.It is organic molten that solution A by organosilan is dissolved in first
Agent prepares to obtain, wherein the first organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydrofuran, dichloro
Methane or toluene, the concentration of organosilan is 0.1~5mol/L in solution A.
Preferably, step (1) described organosilan is methyldiphenyl base silane, tri-phenyl-silane, triethylsilane, two uncles
Butylsilane, dimethylbenzyl base silane.
Step (2) described oxidant is tert-butyl hydroperoxide, cumyl peroxide, dibenzoyl peroxide, peroxide
Change t-butyl perbenzoate, sodium peroxide, potassium peroxide or hydrogen peroxide.Solution B is dissolved in the second organic solvent with obtained by oxidant
Arrive, wherein the second organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydrofuran, dichloromethane or first
Benzene, the concentration of oxidant is 0.01~5mol/L in solution B.
Preferably, the concentration of organosilan is 0.2~0.5mmol/L in step (1) described solution A；Step (2) is described molten
The concentration of oxidant is 0.06~0.15mmol/L in liquid B.
The catalyst filled in step (3) described microreactor is stannous chloride, copper chloride, copper sulphate or copper.It is described molten
The molar ratio of organosilan and oxidant in the solution B is 1 in liquid A:0.1~1；Preferably, molar ratio 10:3.It is described micro-
Reaction temperature in reactor is 70~150 DEG C, and reaction time is 10~120min；Wherein, solution A and solution B are through micro-
Flow velocity after mixer mixing in microreactor is 0.01~10mL/min；Preferably, the reaction temperature in the microreactor
Spend for 100~120 DEG C, reaction time is 10~30min, and flow velocity is 0.15~0.45mL/min.
The micro-reaction device includes micro-mixer, microreactor and the counterbalance valve by connecting tube sequential series, described
The feed inlet of micro-mixer has 2, including solution A feed inlet and solution B feed inlet, solution A feed inlet and solution B feed inlet point
It is not connected with feed pump；The micro-mixer is Y types, T-shaped or J-type；The microreactor is cylindrical reactor, the column
The internal diameter of reactor is 0.5~5mm, and length is 0.5~40m.The pressure of the counterbalance valve is 6~14bar.
Beneficial effect：Compared with prior art, technical advantage of the invention is as follows：
(1) the required raw material of the present invention is easy to get and stability is good, is taken by the use of metallic copper class compound as catalyst to three
Coupling reaction is carried out for silane, base metal catalysts and transiting state metal catalyst are better than to the coupling effect of three substituted silanes；
Micro passage reaction is because of its good mixing and heat transfer property, suitable for exothermic coupling reaction.
(2) compared with traditional tank reactor, microreactor system relative closure, it is not easy to be subject to water, air etc. because
The influence of element, can reduce influence of these factors to silane.Microreactor system reaction condition is gentle, and reaction conversion ratio is higher,
Accessory substance is few, and product quality is high.Loss of the agents useful for same to equipment is low, can continuously continual be produced.Meanwhile this hair
Bright method is easy to operate, and environmental pollution is small, has good prospects for commercial application.
Brief description of the drawings
Fig. 1 is the reaction process schematic diagram of the present invention；
Fig. 2 is methyldiphenyl base silane product1HNMR collection of illustrative plates；
Fig. 3 is dimethyl benzyl silane product1HNMR collection of illustrative plates.
Embodiment
Embodiment 1
10g stannous chlorides are filled in column microreactor, microreactor internal diameter is 2mm, length 0.5m.Take
0.99g (5mmol) methyldiphenyl base silane is dissolved in 10mLN, obtains solution of silane in dinethylformamide, takes 0.135g
(1.5mmol) tert-butyl hydroperoxide is dissolved in 10mLN, and oxidizing agent solution is obtained in dinethylformamide.By solution of silane with
Oxidizing agent solution passes through T-shaped mixer 1:After 1 mixing, then it is passed into 100 DEG C of column microreactor and reacts, control pump sample introduction
Speed be 0.45mL/min, reaction time 10min, the pressure of counterbalance valve is 6bar.Reaction carries out a cycle
After pick up 4.5mL reaction solutions, separate and purified product, obtain product 0.21g, yield 95%.
Embodiment 2
Preparation method, the difference is that catalyst is 10g copper chlorides, finally obtains product 0.18g, yield is with embodiment 1
85%.
Embodiment 3
Preparation method, the difference is that catalyst is 10g copper powders, finally obtains product 0.20g, yield is with embodiment 1
90%.
Embodiment 4
Preparation method, the difference is that organosilan is 1.30g (5mmol) tri-phenyl-silane, finally obtains production with embodiment 1
Thing 0.28g, yield 96%.
Embodiment 5
Preparation method is with embodiment 1, the difference is that organosilan is 0.68g (5mmol) dimethylphenylsilaneand, final
To product 0.14g, yield 89%.
Embodiment 6
Preparation method, the difference is that organosilan is 0.58g (5mmol) triethylsilane, finally obtains production with embodiment 1
Thing 0.12g, yield 86%.
Embodiment 7
Preparation method, the difference is that organosilan is 0.72g (5mmol) di-t-butyl silane, is finally obtained with embodiment 1
Product 0.15g, yield 92%.
Embodiment 8
Preparation method is with embodiment 1, the difference is that organosilan is 0.75g (5mmol) dimethylbenzyl base silane, final
To product 0.15g, yield 90%.
Embodiment 9
Preparation method is with embodiment 1, the difference is that methyldiphenyl base silane is dissolved in n,N-dimethylacetamide, the tert-butyl group
Hydrogen peroxide is dissolved in n,N-dimethylacetamide, finally obtains product 0.17g, yield 79%.
Embodiment 10
Preparation method is with embodiment 1, the difference is that methyldiphenyl base silane is dissolved in tetrahydrofuran, tert-butyl hydroperoxide
It is dissolved in tetrahydrofuran, finally obtains product 0.16g, yield 72%.
Embodiment 11
Preparation method is with embodiment 1, the difference is that methyldiphenyl base silane is dissolved in dichloromethane, tert-butyl hydroperoxide
It is dissolved in dichloromethane, finally obtains product 0.15g, yield 68%.
Embodiment 12
Preparation method is with embodiment 1, the difference is that oxidant is 0.40g (1.5mmol) cumyl peroxide, final
To product 0.17g, yield 79%.
Embodiment 13
Preparation method is with embodiment 1, the difference is that oxidant is 0.36g (1.5mmol) dibenzoyl peroxide, final
To product 0.18g, yield 85%.
Embodiment 14
Preparation method is with embodiment 1, the difference is that oxidant is 0.29g (1.5mmol) peroxidized t-butyl perbenzoate, most
Product 0.15g, yield 68% are obtained eventually.
Embodiment 15
Preparation method is with embodiment 1, the difference is that organosilan is 0.40g (2mmol) methyldiphenyl base silane, oxidant
For 0.054g (0.6mmol) tert-butyl hydroperoxide, product 0.08g, yield 89% are finally obtained.
Embodiment 16
Preparation method is with embodiment 1, the difference is that organosilan is 9.90g (50mmol) methyldiphenyl base silane, oxidation
Agent is 1.35g (15mmol) tert-butyl hydroperoxide, finally obtains product 1.60g, yield 72%.
Embodiment 17
Preparation method is with embodiment 1, the difference is that the speed of control pump sample introduction solution A and solution B is 0.15mL/min,
Reaction time is 30min, finally obtains product 0.22g, yield 96%.
Embodiment 18
Preparation method is with embodiment 1, the difference is that the speed of control pump sample introduction solution A and solution B is 0.075mL/
Min, reaction time 60min, finally obtain product 0.22g, yield 96%.
Embodiment 19
Preparation method is with embodiment 1, the difference is that the speed of control pump sample introduction solution A and solution B is 0.038mL/
Min, reaction time 120min, finally obtain product 0.21g, yield 95%.
Embodiment 20
Preparation method, the difference is that mixer is Y type mixers, finally obtains product 0.207g, yield is with embodiment 1
93%.
Embodiment 21
Preparation method, the difference is that the reaction temperature in microreactor is 70 DEG C, finally obtains product with embodiment 1
0.16g, yield 72%.
Embodiment 22
Preparation method, the difference is that the reaction temperature in microreactor is 120 DEG C, finally obtains product with embodiment 1
0.20g, yield 90%.
Embodiment 23
Preparation method, the difference is that the reaction temperature in microreactor is 140 DEG C, finally obtains product with embodiment 1
0.17g, yield 80%.
Embodiment 24
Preparation method is with embodiment 1, the difference is that catalyst is 10g copper sulphate.
Embodiment 25
Preparation method is with embodiment 1, the difference is that methyldiphenyl base silane is dissolved in toluene, tert-butyl hydroperoxide is dissolved in
In toluene.
Embodiment 26
Preparation method is with embodiment 1, the difference is that oxidant is the sodium peroxide of 5mmol.
Embodiment 27
Preparation method is with embodiment 1, the difference is that oxidant is the hydrogen peroxide of 5mmol.
Embodiment 28
Preparation method is with embodiment 1, the difference is that oxidant is the potassium peroxide of 5mmol.
Embodiment 29
Preparation method is with embodiment 1, the difference is that organosilan is 9.9g (50mmol) methyldiphenyl base silane, oxidant
For 4.5g (50mmol) tert-butyl hydroperoxide, reaction temperature is 150 DEG C.
Embodiment 30
Preparation method is with embodiment 1, the difference is that organosilan is 0.2g (1mmol) methyldiphenyl base silane, oxidant
For 0.09g (0.1mmol) tert-butyl hydroperoxide.
Comparative example 1
10g stannous chlorides, 0.99g (5mmol) methyldiphenyl base silane, and 0.135g are added in 50mL single port bottles
(1.5mmol) tert-butyl hydroperoxide, adds 20mL n,N-Dimethylformamide, reaction is stirred under the conditions of 100 DEG C, instead
It is 10min between seasonable.After reaction, 4.5mL reaction solutions are taken, simultaneously purified product is separated, obtains product 0.12g, yield is
54%.
Comparative example 2
In glove box in the case of nitrogen protection, 20mL dry toluenes are added in Schlenk bottles of 50mL, are added
0.99g (5mmol) methyldiphenyl base silanes and 0.23g (10mmol) sodium, 110 DEG C of stirring reaction 2h after sealing.Reaction terminates
Sampling detection afterwards, and it is not detected by target product.
Claims (10)
- A kind of 1. method that disilane class compound is continuously prepared using micro-reaction device, it is characterised in that comprise the following steps：(1) solution A is dissolved in that the first organic solvent is prepared to obtain or solution A is organosilan by organosilan；(2) solution B is dissolved in that the second organic solvent is prepared to obtain or solution B is oxidant by oxidant；(3) micro-mixer being pumped into step (1) solution A and step (2) described solution B at the same time respectively in micro-reaction device In mixed, carry out reaction in the microreactor then flowed into micro-reaction device disilane class compound be prepared；Its In, catalyst filling in the microreactor.
- 2. according to the method described in claim 1, it is characterized in that, step (1) described organosilan is any in compound I It is one or more of；Wherein R1、R2、R3It is each independently selected from aryl or alkyl.
- 3. according to the method described in claim 2, it is characterized in that, step (1) described organosilan for methyldiphenyl base silane, Tri-phenyl-silane, triethylsilane, di-t-butyl silane, dimethylbenzyl base silane.
- 4. according to the method described in claim 1, it is characterized in that, step (2) described oxidant is tert-butyl hydroperoxide, mistake Aoxidize diisopropylbenzene (DIPB), dibenzoyl peroxide, peroxidized t-butyl perbenzoate, sodium peroxide, potassium peroxide or hydrogen peroxide.
- 5. according to the method described in claim 1, it is characterized in that, step (1) solution A is dissolved in first by organosilan has Solvent is prepared to obtain, wherein the first organic solvent for n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydrofuran, Dichloromethane or toluene；Step (2) solution B is dissolved in the second organic solvent by oxidant and prepares to obtain, wherein second is organic Solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran, dichloromethane or toluene.
- 6. according to the method described in claim 5, it is characterized in that, the concentration of organosilan is in step (1) described solution A 0.1~5mol/L；The concentration of oxidant is 0.01~5mol/L in step (2) described solution B.
- 7. according to the method described in claim 1, it is characterized in that, the catalyst filled in step (3) described microreactor is Stannous chloride, copper chloride, copper sulphate or copper.
- 8. according to the method described in claim 1, it is characterized in that, organosilan and step (2) in step (1) described solution A The molar ratio of oxidant is 1 in the solution B:0.1~1.
- 9. according to the method described in claim 1, it is characterized in that, the reaction temperature in step (3) described microreactor is 70 ~150 DEG C, reaction time is 10~120min.
- 10. according to the method described in claim 1, it is characterized in that, step (3) described microreactor is cylindrical reactor, institute The internal diameter for stating cylindrical reactor is 0.5~5mm, and length is 0.5~40m.
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| CN110669066A (en) * | 2019-10-15 | 2020-01-10 | 徐州医科大学 | Disilane and preparation method thereof |
| CN112110950A (en) * | 2020-08-17 | 2020-12-22 | 杭州师范大学 | Preparation method of disilane |
| CN114621279A (en) * | 2022-04-19 | 2022-06-14 | 湖南农业大学 | Preparation method for aryl silane dimer compound through aryl silane self-coupling synthesis under photocatalysis |
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| CN108821951A (en) * | 2018-07-16 | 2018-11-16 | 中国药科大学 | A kind of method for breaking using ehter bond in micro-reaction device continuous catalysis lignin monomer structure |
| CN108821951B (en) * | 2018-07-16 | 2021-08-13 | 中国药科大学 | Method for continuously catalyzing ether bond fracture in lignin monomer structure by using micro-reaction device |
| CN109748932A (en) * | 2019-01-09 | 2019-05-14 | 浙江新化化工股份有限公司 | A kind of continuous synthesis method of hexamethyldisilazane |
| CN109748932B (en) * | 2019-01-09 | 2021-06-08 | 浙江新化化工股份有限公司 | Continuous synthesis method of hexamethyldisilazane |
| CN110669066A (en) * | 2019-10-15 | 2020-01-10 | 徐州医科大学 | Disilane and preparation method thereof |
| CN110669066B (en) * | 2019-10-15 | 2022-04-19 | 徐州医科大学 | Disilane and preparation method thereof |
| CN112110950A (en) * | 2020-08-17 | 2020-12-22 | 杭州师范大学 | Preparation method of disilane |
| CN112110950B (en) * | 2020-08-17 | 2023-02-14 | 杭州师范大学 | Preparation method of disilane |
| CN114621279A (en) * | 2022-04-19 | 2022-06-14 | 湖南农业大学 | Preparation method for aryl silane dimer compound through aryl silane self-coupling synthesis under photocatalysis |
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