CN106831850B - A kind of hydrosilylation - Google Patents
A kind of hydrosilylation Download PDFInfo
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- CN106831850B CN106831850B CN201611099849.4A CN201611099849A CN106831850B CN 106831850 B CN106831850 B CN 106831850B CN 201611099849 A CN201611099849 A CN 201611099849A CN 106831850 B CN106831850 B CN 106831850B
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- hydrosilylation
- isonitrile base
- silane
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- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 229910000077 silane Inorganic materials 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 150000002527 isonitriles Chemical class 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 51
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 23
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- UWGIJJRGSGDBFJ-UHFFFAOYSA-N dichloromethylsilane Chemical compound [SiH3]C(Cl)Cl UWGIJJRGSGDBFJ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 24
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000000047 product Substances 0.000 description 22
- 229920002545 silicone oil Polymers 0.000 description 21
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- -1 trichlorosilane alkane Chemical class 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- 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
- C07F7/12—Organo silicon halides
- C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The present invention relates to organic chemistry fileds, to solve the problems, such as that catalyst exists at high cost due to using noble metal to cause in hydrosilylation of olefins, the invention proposes a kind of hydrosilylations, using alkene and silane containing hydrogen as raw material, hydrosilylation is carried out under the action of catalyst, a kind of divalent metal salt of straight chain fatty carboxylic acid of the catalyst selected from end position for isonitrile base, structural formula is M [CN (CH2)nCOO]2, wherein M=Fe, Co, n=3,5,6,10, catalyst used in the present invention is iron, cobalt salt class complex, and cheap, preparation is simple.
Description
Technical field
The present invention relates to organic chemistry filed, specifically a kind of hydrosilylation.
Background technique
Hydrosilylation of olefins be construct C-Si key important method, synthesizing silane coupler, organosilicon macromolecule,
And function organo-silicon compound etc. are widely used.Usual hydrosilylation of olefins uses the precious metals such as platinum, rhodium, ruthenium
Complex makees catalyst, such as industry at present and laboratory usually using Speier catalyst (aqueous isopropanol of chloroplatinic acid) and
Karstedt catalyst (the tetramethyl divinyl disiloxane complex of platinum), exist catalytic activity is lower, product with urge
The disadvantages of agent separation is difficult, poor to substrate universality, catalyst is at high cost (J.Organomet.Chem., 2003,681,91-
97).For this purpose, vast researcher explores the application including the Non-precious Metal Catalysts alkene Si―H addition reaction such as iron, cobalt, but it is made
Preparation Method it is complicated (Tondreau AM, et al Science, 2012,335,567；Chen C,et al
J.Am.Chem.Soc.,2015,137,13244)。
Summary of the invention
To solve the problems, such as in hydrosilylation of olefins that catalyst exists due at high cost, this hair that uses noble metal to cause
Bright to propose a kind of hydrosilylation, catalyst used in the present invention is iron, cobalt salt class complex, cheap, preparation
Simply.
The present invention is achieved by the following technical solutions: a kind of hydrosilylation, is original with alkene and silane containing hydrogen
Material, carries out hydrosilylation under the action of catalyst, and the catalyst is the straight chain fatty of isonitrile base selected from a kind of end position
The divalent metal salt of carboxylic acid, structural formula are M [CN (CH2)nCOO]2, wherein M=Fe, Co, n=3,5,6,10.Straight chained alkyl chain length
By the chain length of change aliphatic chain, its catalytic performance is adjusted, thus there is certain influence on the catalytic performance of hydrosilylation.
Preferably, the divalent metal salt is selected from one of ferrous salt, cobalt salt.
Preferably, end position is different selected from 3- isonitrile base butyric acid, 6- isonitrile base caproic acid, 7- for the straight chain fatty carboxylic acid of isonitrile base
One of itrile group enanthic acid, 11- isonitrile base undecanoic acid.
The alkene is selected from one of 1- hexene, 1- octene, 1- decene, styrene, and the silane containing hydrogen is selected from
One of triethoxy hydrogen silane, dichloromethylsilane, trichlorosilane alkane, triethylsilane.
The reaction process of hydrosilylation are as follows: in the reactor, catalyst, alkene and silane containing hydrogen is added, seals, so
After be to slowly warm up to 50~90 DEG C, keep reaction temperature, continue to be stirred to react, be analyzed by gas-chromatography, reaction terminates
After stand, be cooled to room temperature.
Preferably, the molar ratio of alkene, silane containing hydrogen, catalyst is 100:110~120:0.05~0.5, more preferably
Molar ratio be 100:110:0.1.
Compared with prior art, it is simple that the beneficial effects of the invention are as follows catalyst preparations, at low cost, and reaction condition is mild,
Substrate universality is wide.
Specific embodiment
Below by specific embodiment, technical solution of the present invention is further described in detail, catalyst passes through following
Method preparation.
By taking 11- isonitrile base undecane-carboxylic acid ferrous salt as an example, preparation process is as follows
In 250mL three-necked flask, 100mL formic acid, 11- amido hendecanoic acid (20.1g, 0.1mol), 0.1g chlorination is added
Zinc, stirring, is heated to reflux 2h, steams formic acid, 100mL deionized water is added after cooling, 50mL sodium hydroxide water is added dropwise under stirring
Solution (4.0g containing NaOH) continues to stir 2h after dripping.By its with dissolved with FeCl2·4H2O (9.94g, 0.05mol's) goes
Ionized water 50mL mixing is heated with stirring to 80 DEG C, and 30 minutes, cooling, suction filtration, deionization is washed, and acetone is washed, and is dried in vacuo, is obtained
Solid product 22.8g.
Above-mentioned solid product 9.6g is suspended in 100mL anhydrous tetrahydro furan, triethylamine 30mL, nitrogen protection is added
Under, the tetrahydrofuran 25mL of 4.5mL containing phosphorus oxychloride (48mmol) is added dropwise, drips recession and removes ice bath, continues stirring 1 hour,
It is slowly added to 50mL ice water, is filtered, is washed to washing lotion and is in neutrality, acetone is washed, and it is dried in vacuo 20 hours, obtains solid product 8.2g,
It is denoted as Fe [CN (CH2)10COO]2。
Replacing 11- amido hendecanoic acid with gaba, 6- amidcaproic acid, 7- amido enanthic acid respectively is raw material, is taken
Same steps can be made corresponding end position isonitrile base straight chain fatty carboxylic acid ferrous salt, be denoted as Fe [CN (CH respectively2)3COO]2、
Fe[CN(CH2)5COO]2、Fe[CN(CH2)6COO]2。
Use CoCl2·6H2O replaces FeCl2·4H2End position isonitrile base straight chain rouge can be made using the above method in O respectively
Fat carboxylic acid cobalt salt is denoted as Co [CN (CH respectively2)10COO]2、Co[CN(CH2)3COO]2、Co[CN(CH2)5COO]2、Co[CN
(CH2)6COO]2。
Embodiment 1
476mg(1.0mmol)Fe[CN(CH2)10COO]2, 1mol styrene and 1.1mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 8h is reacted in 80 DEG C of silicone oil baths, styrene conversion rate is that 75.7%, β addition product is selectively 90.4%.
Embodiment 2
476mg(1.0mmol)Fe[CN(CH2)10COO]2, 1mol 1- hexene and 1.1mol triethoxy hydrogen silane are placed in
In pressure reaction still, 4h is reacted in 80 DEG C of silicone oil baths, 1- hexene conversion ratio is that 99.5%, β addition product is selectively 99.2%.
Embodiment 3
Take 476mg (1.0mmol) Fe [CN (CH2)10COO]2, 1mol 1- octene and 1.1mol triethoxy hydrogen silane are set
In in pressure reaction still, reacting 4h in 80 DEG C of silicone oil baths, 1- octene conversion is that 97.3%, β addition product is selectively
99.5%.
Embodiment 4
Take 476mg (1.0mmol) Fe [CN (CH2)10COO]2, 1mol 1- hexene and 1.1mol dichloromethylsilane are set
In in pressure reaction still, reacting 4h in 80 DEG C of silicone oil baths, 1- hexene conversion ratio is that 98.5%, β addition product is selectively
99.2%.
Embodiment 5
476mg(1.0mmol)Fe[CN(CH2)10COO]2, 1mol 1- octene and 1.1mol dichloromethylsilane are placed in
In pressure reaction still, 4h is reacted in 80 DEG C of silicone oil baths, 1- octene conversion is that 98.5%, β addition product is selectively 99.2%.
Embodiment 6
238mg(0.5mmol)Fe[CN(CH2)10COO]2, 1mol 1- hexene and 1.1mol triethoxy hydrogen silane are placed in
In pressure reaction still, 4h is reacted in 80 DEG C of silicone oil baths, 1- hexene conversion ratio is that 89.5%, β addition product is selectively 99.5%.
Embodiment 7
280mg(1.0mmol)Fe[CN(CH2)3COO]2, 1mol 1- octene and 1.1mol dichloromethylsilane are placed in pressure
In power reaction kettle, 4h is reacted in 80 DEG C of silicone oil baths, 1- octene conversion is that 88.7%, β addition product is selectively 98.5%.
Embodiment 8
336mg(1.0mmol)Fe[CN(CH2)5COO]2, 1mol 1- octene and 1.1mol dichloromethylsilane are placed in pressure
In power reaction kettle, 4h is reacted in 80 DEG C of silicone oil baths, 1- octene conversion is that 89.6%, β addition product is selectively 98.9%.
Embodiment 9
364mg(1.0mmol)Fe[CN(CH2)6COO]2, 1mol 1- octene and 1.1mol dichloromethylsilane are placed in pressure
In power reaction kettle, 4h is reacted in 80 DEG C of silicone oil baths, 1- octene conversion is that 91.6%, β addition product is selectively 99.0%.
Embodiment 10
Take 476mg (1.0mmol) Fe [CN (CH2)10COO]2, 1mol 1- hexene and 1.1mol triethyl group hydrogen silane are placed in
In pressure reaction still, 4h is reacted in 80 DEG C of silicone oil baths, 1- hexene conversion ratio is that 97.5%, β addition product is selectively 99.4%.
Embodiment 11
476mg(1.0mmol)Fe[CN(CH2)10COO]2, 1mol 1- decene and 1.1mol triethoxysilane are placed in pressure
In power reaction kettle, 4h is reacted in 80 DEG C of silicone oil baths, 1- decene conversion ratio is that 95.5%, β addition product is selectively 99.6%.
Embodiment 12
476mg(1.0mmol)Fe[CN(CH2)10COO]2, 1mol 1- decene and 1.1mol triethoxysilane are placed in pressure
In power reaction kettle, 4h is reacted in 90 DEG C of silicone oil baths, 1- decene conversion ratio is that 98.5%, β addition product is selectively 99.7%.
Embodiment 13
479mg(1.0mmol)Co[CN(CH2)10COO]2, 1mol styrene and 1.1mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 8h is reacted in 80 DEG C of silicone oil baths, styrene conversion rate is that 85.7%, β addition product is selectively 87.4%.
Embodiment 14
479mg(1.0mmol)Co[CN(CH2)10COO]2, 1mol 1- hexene and 1.1mol triethoxy hydrogen silane are placed in
In pressure reaction still, 4h is reacted in 80 DEG C of silicone oil baths, 1- hexene conversion ratio is that 99.7%, β addition product is selectively 99.5%.
Embodiment 15
367mg(1.0mmol)Co[CN(CH2)6COO]2, 1mol 1- hexene and 1.1mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 4h is reacted in 70 DEG C of silicone oil baths, 1- hexene conversion ratio is that 92.7%, β addition product is selectively 98.8%.
Embodiment 16
339mg(1.0mmol)Co[CN(CH2)5COO]2, 1mol 1- hexene and 1.1mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 4h is reacted in 70 DEG C of silicone oil baths, 1- hexene conversion ratio is that 89.5%, β addition product is selectively 98.9%.
Embodiment 17
170mg(0.5mmol)Co[CN(CH2)5COO]2, 1mol 1- hexene and 1.1mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 4h is reacted in 70 DEG C of silicone oil baths, 1- hexene conversion ratio is that 78.6%, β addition product is selectively 99.3%.
Embodiment 18
283mg(1.0mmol)Co[CN(CH2)3COO]2, 1mol 1- hexene and 1.1mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 4h is reacted in 80 DEG C of silicone oil baths, 1- hexene conversion ratio is that 94.3%, β addition product is selectively 98.9%.
Embodiment 19
678mg(2.0mmol)Co[CN(CH2)5COO]2, 1mol 1- hexene and 1.2mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 4h is reacted in 80 DEG C of silicone oil baths, 1- hexene conversion ratio is that 99.4%, β addition product is selectively 99.0%.
Embodiment 20
339mg(1.0mmol)Co[CN(CH2)5COO]2, 1mol 1- hexene and 1.2mol triethoxy hydrogen silane are placed in pressure
In power reaction kettle, 4h is reacted in 90 DEG C of silicone oil baths, 1- hexene conversion ratio is that 99.4%, β addition product is selectively 99.5%.
Embodiment 21
479mg(1.0mmol)Co[CN(CH2)5COO]2, 1mol 1- hexene and 1.15mol triethyl group hydrogen silane are placed in pressure
In power reaction kettle, 4h is reacted in 90 DEG C of silicone oil baths, 1- hexene conversion ratio is that 99.1%, β addition product is selectively 99.7%.
Claims (3)
1. a kind of hydrosilylation, which is characterized in that using alkene and silane containing hydrogen as raw material, carry out silicon under the action of catalyst
Addition reaction of hydrogen, a kind of divalent metal salt of straight chain fatty carboxylic acid of the catalyst selected from end position for isonitrile base are described to urge
The structural formula of agent is M [CN (CH2)nCOO]2, wherein M=Fe, Co, n=3,5,6,10；
Divalent metal salt described in catalyst is selected from one of ferrous salt, cobalt salt, and catalyst middle-end position is the straight of isonitrile base
Chain fatty carboxylic acid is selected from one of 3- isonitrile base butyric acid, 6- isonitrile base caproic acid, 7- isonitrile base enanthic acid, 11- isonitrile base undecanoic acid.
2. a kind of hydrosilylation according to claim 1, which is characterized in that the alkene is selected from 1- hexene, 1-
One of octene, 1- decene, styrene, the silane containing hydrogen are selected from triethoxy hydrogen silane, dichloromethylsilane, three
One of chlorine hydrogen silane, triethylsilane.
3. a kind of hydrosilylation according to claim 1 or 2, which is characterized in that alkene, silane containing hydrogen, catalyst
Molar ratio be 100:110~120:0.05~0.5.
Priority Applications (1)
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| CN107840856B (en) * | 2017-10-27 | 2020-04-21 | 杭州师范大学 | Method for hydrosilylation reaction of olefin and hydrogen-containing silane |
| CN108129507B (en) * | 2017-12-04 | 2020-05-29 | 杭州师范大学 | Hydrosilylation reaction using titanate as catalyst and application thereof |
| CN108033976B (en) * | 2017-12-04 | 2020-09-01 | 杭州师范大学 | Unsaturated compound hydrosilylation reaction using metallocene as catalyst |
| CN110117296B (en) * | 2019-05-13 | 2021-06-15 | 杭州师范大学 | Silicon-based modified isonitrile metal salt catalyst and preparation method and application thereof |
| CN110302831B (en) * | 2019-05-23 | 2021-12-21 | 杭州师范大学 | Silicon-based modified organic carboxylic acid metal salt catalyst and application thereof |
| CN110452259B (en) * | 2019-07-24 | 2022-08-30 | 杭州师范大学 | Method for photoinitiating hydrosilylation reaction |
| CN110465330B (en) * | 2019-08-09 | 2022-06-10 | 杭州师范大学 | Method for hydrosilylation reaction by using cobalt catalyst |
| CN114591375B (en) * | 2022-03-23 | 2024-09-17 | 国科广化精细化工孵化器(南雄)有限公司 | Imidazoline modified iron metal complex and preparation method and application thereof |
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| CN101322946A (en) * | 2008-06-24 | 2008-12-17 | 杭州师范大学 | Hydrosilylation catalyst, preparation method and uses thereof |
| CN104119371A (en) * | 2014-03-26 | 2014-10-29 | 杭州师范大学 | Method for alkene hydrosilylation |
| WO2014198633A1 (en) * | 2013-06-11 | 2014-12-18 | Sika Technology Ag | Curable composition based on polymers containing silane groups and on a zinc catalyst |
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| CN101322946A (en) * | 2008-06-24 | 2008-12-17 | 杭州师范大学 | Hydrosilylation catalyst, preparation method and uses thereof |
| WO2014198633A1 (en) * | 2013-06-11 | 2014-12-18 | Sika Technology Ag | Curable composition based on polymers containing silane groups and on a zinc catalyst |
| CN104119371A (en) * | 2014-03-26 | 2014-10-29 | 杭州师范大学 | Method for alkene hydrosilylation |
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