CN115850330A - Synthesis method of n-butyl di (1-adamantyl) phosphine - Google Patents
Synthesis method of n-butyl di (1-adamantyl) phosphine Download PDFInfo
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- CN115850330A CN115850330A CN202211614185.6A CN202211614185A CN115850330A CN 115850330 A CN115850330 A CN 115850330A CN 202211614185 A CN202211614185 A CN 202211614185A CN 115850330 A CN115850330 A CN 115850330A
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- Prior art keywords
- adamantyl
- butyl
- phosphine
- bis
- reaction
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- HTJWUNNIRKDDIV-UHFFFAOYSA-N bis(1-adamantyl)-butylphosphane Chemical compound C1C(C2)CC(C3)CC2CC13P(CCCC)C1(C2)CC(C3)CC2CC3C1 HTJWUNNIRKDDIV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000001308 synthesis method Methods 0.000 title description 7
- -1 1-adamantyl Chemical group 0.000 claims abstract description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007341 Heck reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGWFDTKFTGTOAF-UHFFFAOYSA-N P.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl DGWFDTKFTGTOAF-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RRRZOLBZYZWQBZ-UHFFFAOYSA-N bis(1-adamantyl)phosphane Chemical compound C1C(C2)CC(C3)CC2CC13PC(C1)(C2)CC3CC2CC1C3 RRRZOLBZYZWQBZ-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000010651 palladium-catalyzed cross coupling reaction Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- DHNUAKOQUGJUGA-UHFFFAOYSA-N silicon;sulfane Chemical compound [Si].S DHNUAKOQUGJUGA-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Abstract
The invention discloses a method for synthesizing n-butyl di (1-adamantyl) phosphine, belonging to the field of organic synthesis. The method is realized by the following steps: under the anhydrous and oxygen-free atmosphere, under the action of triethylamine, bis (1-adamantyl) phosphonyl chloride and n-butyl alcohol generate an intermediate n-butyl bis (1-adamantyl) phosphonate, and under the catalytic action of tetraisopropyl titanate and polymethylsiloxane, the n-butyl bis (1-adamantyl) phosphonate is reduced to generate the target compound n-butyl bis (1-adamantyl) phosphine. Compared with the prior art, the method has the advantages of mild reaction conditions, simple operation, high yield, simple and easily obtained raw materials, and suitability for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, relates to a synthesis method of an organic phosphine compound, and particularly relates to a synthesis method of n-butyl di (1-adamantyl) phosphine.
Technical Field
The n-butyl di (1-adamantyl) phosphine is an important organic phosphine catalyst, has strong electron-rich property, and is widely applied to palladium-catalyzed cross-coupling reactions, such as Heck and Suzuki coupling reactions. In the coupling reaction, the steric and stereo-electronic properties can effectively activate the aryl halogenated reagent. Therefore, the development of an industrial synthesis method of n-butyldi (1-adamantyl) phosphine is of great research significance.
At present, a plurality of synthesis methods are reported for n-butyl di (1-adamantyl) phosphine, but all the synthesis methods have certain limitations and limit the industrial large-scale preparation of the n-butyl di (1-adamantyl) phosphine. For example, the Beller research group reports the formation of bis (1-adamantyl) phosphinite chloride upon hydrolysis by reacting adamantane with phosphine trichloride. The resulting phosphorus (V) compound is then reduced by lithium aluminum hydride to give bis (1-adamantyl) phosphine, which is chlorinated with phosgene (Ehrentraut, A.; zapf, A.; beller, M.Synlett 2000, 1589). Due to the harsh reaction conditions, the repeatability and purity of the reaction are both problematic. The Schmutzler group synthesizes n-butyl bis (1-adamantyl) phosphine by quaternization of bis (1-adamantyl) phosphine hydride with butyl iodide followed by deionization with triethylamine (Goerlich, J.R.; schmutzler, R.Phosphorus, sulfur Silicon Relat. Elem.1995,102, 211). The method uses phosphine reagents with high dangerousness, and limits the wide application of the phosphine reagents. Therefore, there is a need to develop a new synthetic method for preparing n-butyldi (1-adamantyl) phosphine.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing bis (1-adamantyl) n-butylphosphine, which has the advantages of high yield, mild reaction conditions and simple operation.
In order to achieve the above object, the reaction scheme of the present invention is as follows:
adding a reaction solvent tetrahydrofuran into a drying reactor under the protection of argon, then adding bis (1-adamantyl) phosphonyl chloride, n-butyl alcohol and triethylamine, carrying out reflux reaction in the tetrahydrofuran to generate an intermediate n-butyl bis (1-adamantyl) phosphonate, then adding tetraisopropyl titanate and polymethylsiloxane, continuing reflux, stopping the reaction after the reaction is finished, filtering, recrystallizing and drying to obtain n-butyl bis (1-adamantyl) phosphine;
the molar ratio of the bis (1-adamantyl) phosphonyl chloride, the n-butyl alcohol, the triethylamine, the tetraisopropyl titanate and the polymethylsiloxane is (1-1.5).
The invention has the beneficial effects that: the method avoids the use of n-butyllithium or diamantane phosphine hydrogen reagent with higher risk, avoids multi-step reaction and post-treatment, adopts mild triethylamine and easily obtained n-butyl alcohol reagent, directly synthesizes target products by one step without separation, has lower reaction temperature, milder reaction conditions, simpler and more convenient operation, has the yield of more than 85 percent, and is beneficial to actual industrial production.
Detailed Description
The following examples are provided to aid in the further understanding of the invention, but the invention is not limited thereto. Examples are as follows:
example 1:
under the protection of argon, 500mL of tetrahydrofuran serving as a reaction solvent is added into a drying reactor, 352g of bis (1-adamantyl) phosphonyl chloride (compound 2), 148g of n-butanol and 202g of triethylamine are sequentially added, heating and refluxing are carried out for 6 hours, 568g of tetraisopropyl titanate and 232g of polymethylsiloxane are added into the system, the reaction system is cooled to room temperature, and 322g (yield 90%) of target product n-butyl di (1-adamantyl) phosphine (compound 1) is obtained through extraction, drying and recrystallization. Nuclear magnetic data: 1 H NMR(C 6 D 6 )δ0.96(3H,t, 3 J H,H ＝7.3Hz,CH 3 ),1.35–2.03(36H,m,adamantyl-30H,butyl-6H). 13 C NMR(C 6 D 6 ):δ41.3(d, 2 J C,P ＝11.3Hz,C-2),37.4(C-4),36.1(d, 1 J C,P ＝23.5Hz,C-1),33.9(d, 1 J C,P ＝26.2Hz,butyla-CH 2 ),29.1(d, 3 J C,P ＝7.6Hz,C-3),24.9(d, 2 J C,P ＝13.1Hz,butylb-CH 2 ),17.1(d, 3 J C,P ＝21.6Hz,butyl-g-CH 2 ),14.3(butyl-CH 3 )。
example 2:
under the protection of argon, 500mL of tetrahydrofuran serving as a reaction solvent is added into a drying reactor, 352g of bis (1-adamantyl) phosphonyl chloride (compound 2), 111g of n-butyl alcohol and 202g of triethylamine are sequentially added, heating and refluxing are carried out for 6 hours, 568g of tetraisopropyl titanate and 232g of polymethylsiloxane are added into the system, the reaction system is cooled to room temperature, and 304g (yield is 85%) of target product n-butyl di (1-adamantyl) phosphine (compound 1) is obtained through extraction, drying and recrystallization.
Example 3:
under the protection of argon, 500mL of tetrahydrofuran serving as a reaction solvent is added into a drying reactor, 352g of bis (1-adamantyl) phosphonyl chloride (compound 2), 148g of n-butanol and 303g of triethylamine are sequentially added, heating and refluxing are carried out for 6 hours, 568g of tetraisopropyl titanate and 232g of polymethylsiloxane are added into the system, the reaction system is cooled to room temperature, and 326g (yield 91%) of target product n-butyl di (1-adamantyl) phosphine (compound 1) is obtained through extraction, drying and recrystallization.
Claims (2)
1. A method for synthesizing n-butyl di (1-adamantyl) phosphine with the structural formula shown as the following, the method is characterized by comprising the following steps:
under the protection of argon, adding a reaction solvent tetrahydrofuran into a drying reactor, then adding bis (1-adamantyl) phosphonyl chloride, n-butyl alcohol and triethylamine, carrying out reflux reaction in the tetrahydrofuran to generate an intermediate n-butyl bis (1-adamantyl) phosphonate, then adding tetraisopropyl titanate and polymethylsiloxane for continuous reflux, stopping the reaction after the reaction is finished, filtering, recrystallizing and drying to obtain n-butyl bis (1-adamantyl) phosphine;
2. the method for synthesizing n-butyldi (1-adamantyl) phosphine according to claim 1, wherein the molar ratio of the bis (1-adamantyl) phosphonyl chloride, n-butanol, triethylamine, tetraisopropyl titanate and polymethylsiloxane is 1:1 to 1.5:2 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211614185.6A CN115850330A (en) | 2022-12-15 | 2022-12-15 | Synthesis method of n-butyl di (1-adamantyl) phosphine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211614185.6A CN115850330A (en) | 2022-12-15 | 2022-12-15 | Synthesis method of n-butyl di (1-adamantyl) phosphine |
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| Publication Number | Publication Date |
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| CN115850330A true CN115850330A (en) | 2023-03-28 |
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| CN202211614185.6A Pending CN115850330A (en) | 2022-12-15 | 2022-12-15 | Synthesis method of n-butyl di (1-adamantyl) phosphine |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040068131A1 (en) * | 2000-07-27 | 2004-04-08 | Matthias Beller | Production of novel phosphane ligands and use in catalytical reactions |
| CN101195641A (en) * | 2007-09-30 | 2008-06-11 | 埃沃尼克德古萨有限责任公司 | Novel phosphine ligand, production and uses in catalytic reaction thereof |
| CN105237461A (en) * | 2015-10-21 | 2016-01-13 | 山东盛华电子新材料有限公司 | Method for utilizing recyclable modified palladium-charcoal to synthesize heterocyclic compound by directly coupling halogenated compound Grignard reagent to halogenated compound |
-
2022
- 2022-12-15 CN CN202211614185.6A patent/CN115850330A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040068131A1 (en) * | 2000-07-27 | 2004-04-08 | Matthias Beller | Production of novel phosphane ligands and use in catalytical reactions |
| CN101195641A (en) * | 2007-09-30 | 2008-06-11 | 埃沃尼克德古萨有限责任公司 | Novel phosphine ligand, production and uses in catalytic reaction thereof |
| CN105237461A (en) * | 2015-10-21 | 2016-01-13 | 山东盛华电子新材料有限公司 | Method for utilizing recyclable modified palladium-charcoal to synthesize heterocyclic compound by directly coupling halogenated compound Grignard reagent to halogenated compound |
Non-Patent Citations (1)
| Title |
|---|
| LI, CHONG ET AL.: "Heck Reaction Boosted Heterocycle Ring-Closing and Ring-Opening Rearrangement: A Strategy for the Synthesis of Indolyl-Type Ligands", JOURNAL OF ORGANIC CHEMISTRY, vol. 86, no. 23, 31 December 2021 (2021-12-31), pages 16977 - 16991 * |
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