CN108484655B - Synthetic method of N-heterocyclic carbene borane adduct - Google Patents
Synthetic method of N-heterocyclic carbene borane adduct Download PDFInfo
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- 229910000085 borane Inorganic materials 0.000 title claims abstract description 25
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 title claims abstract description 15
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 3
- -1 silane compound Chemical class 0.000 claims description 11
- 229910015900 BF3 Inorganic materials 0.000 claims description 10
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 2
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- YXMVRBZGTJFMLH-UHFFFAOYSA-N butylsilane Chemical compound CCCC[SiH3] YXMVRBZGTJFMLH-UHFFFAOYSA-N 0.000 description 4
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FJWMUAQZNQPQRC-UHFFFAOYSA-N B(F)(F)F.C(CCC)N1CN(C=C1)C Chemical compound B(F)(F)F.C(CCC)N1CN(C=C1)C FJWMUAQZNQPQRC-UHFFFAOYSA-N 0.000 description 1
- NWCAEIXQARGINK-UHFFFAOYSA-N B.C1(=CC=CC=C1)N1CN(C=C1)C1=CC=CC=C1 Chemical class B.C1(=CC=CC=C1)N1CN(C=C1)C1=CC=CC=C1 NWCAEIXQARGINK-UHFFFAOYSA-N 0.000 description 1
- DWFCUKVTPQTSTD-UHFFFAOYSA-N B.CN1CN(C=C1)CCCC Chemical compound B.CN1CN(C=C1)CCCC DWFCUKVTPQTSTD-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KFDXCXLJBAVJMR-UHFFFAOYSA-N dibutylsilane Chemical compound CCCC[SiH2]CCCC KFDXCXLJBAVJMR-UHFFFAOYSA-N 0.000 description 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a synthetic method of an N-heterocyclic carbene borane adduct, which comprises the following steps: adding x mol of reaction substrate NHC-BF into a reaction bottle under the protection of inert gas32x-4xL of reaction solvent, x-6x mol of reducing agent hydrosilane, 0.05-0.1x mol of catalyst trifluorophenylboron (BCF), continuously stirring and reacting for 30-60min at 25-50 ℃ under the protection of inert gas after the reactants are added, and NHC-BF3Complete conversion to NHC-BH3And x ranges from 0.001 to 1. The method can be carried out under mild conditions, can completely react within 30-60min, and has high reaction efficiency. The invention has good reaction specificity, no side reaction and reaction yield close to 100%.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthetic method of N-heterocyclic carbene borane adducts.
Background
N-Heterocyclic carbenes (NHC) are a new class of strong sigma electron donors developed at the end of the last century. Compared with the traditional amine, ether and phosphorus ligands, the N-heterocyclic carbene as a ligand has stable property and is insensitive to air and water; the structure is diversified and easy to modify; the electron donating ability is strong, and the coordination bond is not easy to break; low toxicity, simple preparation, low cost and the like. Due to the characteristics of the N-heterocyclic carbene, the N-heterocyclic carbene has wide application in the aspects of homogeneous catalysis, novel materials, antibacterial drugs and the like.
N-heterocyclic carbene borane adducts (NHC-BH)3) Is a highly active carbene adduct which is researched and reported more in recent years. NHC-BH3Can be used for organic synthesis with some alkynes and alkenes through hydroboration reaction; NHC-BH3Some of the derivatives of (a) may also act as initiators for the polymerization of acrylates; more recently, NHC-BH has been reported3Can be used as natural fuel componentIn a natural propellant.
NHC-BH3Has wide potential application value, and NHC-BH is synthesized at present3The method of (2) is limited and the reaction efficiency is low.
The literature (DOI:10.1021/acs.joc.5b01682) reports that NHC-BH3The synthesis method comprises the following steps: reacting dialkyl imidazole salt with sodium borohydride in toluene solution at 125-130 ℃ for 18-24 hours to prepare NHC-BH3The reaction formula is as follows:
although this reaction can be used to prepare NHC-BH in only one step3However, the reaction time is long, the reaction temperature is high, and the reaction yield is only 30-70%.
Another NHC-BH reported in the literature (DOI:10.1021/jo101301d)3The synthesis method comprises the following steps: dialkyl imidazolium salts with strong bases (Me)3Si)2NH. Na reacts in THF solution at-78 deg.C for 1 hr to obtain free NHC, and BH is added into the solution3The reaction is carried out at-78 ℃ for a whole day and night to prepare NHC-BH3The reaction formula is as follows:
the process needs to be carried out at low temperatures of-78 ℃ and dangerous BH is used in the reaction3The reaction time of the gas solution is 12-24 hours, and the yield is only 30-50%.
Disclosure of Invention
In order to solve the problems, the invention provides a synthesis method of N-heterocyclic carbene borane adducts, which can completely react within 30-60min and has high reaction efficiency.
In order to achieve the purpose, the invention adopts the technical scheme that:
a synthetic method of N-heterocyclic carbene borane adducts comprises the following steps:
adding x mol of trans-product into a reaction bottle under the protection of inert gasSubstrate NHC-BF32x-4xL of reaction solvent, x-6x mol of reducing agent hydrosilane, 0.05-0.1x mol of catalyst tris (pentafluorophenyl) Boron (BCF), continuously stirring and reacting for 30-60min at 25-50 ℃ under the protection of inert gas after the reactants are added, and NHC-BF3Complete conversion to NHC-BH3And x ranges from 0.001 to 1.
Preferably, the inert gas is high-purity N2Or high purity Ar gas.
Preferably, the reaction substrate NHC-BF3Wherein NHC represents an N-heterocyclic carbene; alkyl R in NHC1、R2Respectively as follows: methyl, ethyl, isopropyl, n-propyl, n-butyl, phenyl, or the like.
Preferably, the reaction solvent is an aprotic solvent, such as: dichloromethane, chloroform, toluene, benzene, chlorobenzene, etc., preferably dichloromethane, chloroform, toluene.
Preferably, the hydrosilane is a Si-H containing silane compound such as: phenylsilane, butylsilane, ethylsilane, diphenylsilane, dibutylsilane, diethylsilane, silane and the like, with phenylsilane and butylsilane being preferred.
Wherein, the NHC-BF3Dialkyl imidazole boron trifluoride carbene adducts, which can be efficiently prepared by vacuum pyrolysis using ionic liquid (alkyl imidazole tetrafluoroborate), have been reported in the literature, and the reaction equation is as follows:
the invention has the following beneficial effects:
1. can be carried out under mild conditions, can react completely within 30-60min, and has high reaction efficiency.
2. The reaction specificity is good, no side reaction is caused, and the reaction yield is close to 100%.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Preparation of 1, 3-dimethyl imidazole borane adduct
The reaction was carried out under Ar protection, 0.006mol of 1, 3-dimethylimidazole boron trifluoride adduct, 20mL of chloroform, 0.012mol of phenylsilane, and 0.0003mol of tris (pentafluorophenyl) boron catalyst were charged into a 50mL reaction flask, and after the addition of the reactants was completed, the reaction was stirred at 40 ℃ under Ar protection for 50min, NHC-BF3Complete conversion to NHC-BH3。
Example 2
Preparation of 1-methyl-3-ethylimidazole borane adduct
The reaction is carried out under the protection of Ar, 0.01mol of 1-methyl-3-ethylimidazole boron trifluoride adduct, 30mL of toluene, 0.02mol of butylsilane and 0.0005mol of tris (pentafluorophenyl) boron catalyst are added into a 50mL reaction flask, and after the addition of the reactants is finished, the reaction is stirred for 40min under the protection of Ar at 40 ℃, and NHC-BF3Complete conversion to NHC-BH3。
Example 3
Preparation of 1-methyl-3-butylimidazole borane adduct
The reaction is carried out under the protection of Ar, 0.5mol of 1-methyl-3-butylimidazole boron trifluoride adduct, 300mL of dichloromethane, 1mol of butylsilane and 0.025mol of tris (pentafluorophenyl) boron catalyst are added into a 500mL reaction flask, and after the addition of the reactants is finished, the reaction is stirred at the temperature of 35 ℃ under the protection of Ar for 60min, and NHC-BF3Complete conversion to NHC-BH3。
Example 4
Preparation of 1, 3-diisopropylimidazole borane adduct
Reaction in N2Under protection, 0.2mol of 1, 3-diisopropylimidazole boron trifluoride adduct, 300mL of dichloromethane, 1mol of diethylsilane, 0.001mol of tris (pentafluorophenyl) boron catalyst were charged into a 500mL reaction flask, and after completion of the addition of the reactants, the mixture was stirred under N2Stirring and reacting for 45min at the protection temperature of 45 ℃, and performing NHC-BF reaction3Complete conversion to NHC-BH3。
Example 5
Preparation of 1, 3-diphenylimidazole borane adducts
Reaction in N2Under protection, 0.3mol of 1, 3-diphenylimidazole boron trifluoride adduct, 300mL of chloroform, 0.4mol of phenylsilane, and 0.010mol of tris (pentafluorophenyl) boron catalyst were charged into a 500mL reaction flask, and after completion of the addition of the reactants, N was added2Stirring and reacting at the temperature of 40 ℃ for 35min under the protection of NHC-BF3Complete conversion to NHC-BH3。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (5)
1. A synthetic method of N-heterocyclic carbene borane adducts is characterized by comprising the following steps:
adding xmol reaction substrate NHC-BF into a reaction bottle under the protection of inert gas32x-4xL of reaction solvent, x-6x mol of reducing agent hydrosilane, (0.05-0.1) x mol of catalyst tris (pentafluorophenyl) boron, reactingAfter the addition of the substances is finished, under the protection of inert gas, the mixture is continuously stirred and reacts for 30-60min at the temperature of 25-50 ℃, and NHC-BF3Complete conversion to NHC-BH3And x ranges from 0.001 to 1.
2. The method of synthesizing an N-heterocyclic carbene borane adduct of claim 1, wherein the inert gas is high purity N2Or high purity Ar gas.
3. The method of claim 1, wherein the substrate NHC-BF is synthesized as a reaction product3Is 1, 3-dialkyl imidazole-2-boron trifluoride adduct, and the alkyl group of the adduct is methyl, ethyl, isopropyl, n-propyl, n-butyl or phenyl.
4. The method of synthesizing an N-heterocyclic carbene borane adduct of claim 1, wherein the reaction solvent is an aprotic solvent.
5. The method of synthesizing an N-heterocyclic carbene borane adduct of claim 1, wherein the hydrosilane is a Si-H containing silane compound.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772297A (en) * | 2014-01-26 | 2014-05-07 | 上海工程技术大学 | Chiral hexahydroxy n-heterocyclic carbine precursor compound as well as preparation method and application thereof |
| JP2016055217A (en) * | 2014-09-05 | 2016-04-21 | 富士フイルムファインケミカルズ株式会社 | Diborane removal method and diborane remover |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772297A (en) * | 2014-01-26 | 2014-05-07 | 上海工程技术大学 | Chiral hexahydroxy n-heterocyclic carbine precursor compound as well as preparation method and application thereof |
| JP2016055217A (en) * | 2014-09-05 | 2016-04-21 | 富士フイルムファインケミカルズ株式会社 | Diborane removal method and diborane remover |
Non-Patent Citations (2)
| Title |
|---|
| An overview of N-heterocyclic carbenes;Matthew N. Hopkinson等;《Nature》;20140626;第510卷;10294-10317 * |
| Synthesis and Reactions of N-Heterocyclic Carbene Boranes;Dennis P. Curran等;《Angew. Chem. Int. Ed.》;20110907;第50卷;485-496 * |
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