CN111423307A - Reduction method of 2,2,4, 4-tetramethylcyclobutane - Google Patents

Reduction method of 2,2,4, 4-tetramethylcyclobutane Download PDF

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CN111423307A
CN111423307A CN202010423832.XA CN202010423832A CN111423307A CN 111423307 A CN111423307 A CN 111423307A CN 202010423832 A CN202010423832 A CN 202010423832A CN 111423307 A CN111423307 A CN 111423307A
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tetramethyl
binap
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tetramethylcyclobutanedione
catalyst
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郑彬
张占超
汤红仙
张猛
浦忠威
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Shanghai Weixi Pharmaceutical Technology Co ltd
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Abstract

The invention discloses a reduction method of 2,2,4, 4-tetramethyl-cyclobutanedione, which comprises the steps of adding triethylamine into a 2000ml four-neck flask which is provided with a mechanical stirrer, a reflux condenser, an inert gas inlet pipe, a thermometer and a dropping funnel, cooling by using an ice bath, dropwise adding formic acid, adding 2,2,4, 4-tetramethyl-cyclobutanedione, DMF and a catalyst at normal temperature, stirring, filtering, dissolving a filter cake by using methanol, cooling to 0 ℃, and filtering to obtain 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol. The invention utilizes the Ru-Binap system of Noyori to reduce 2,2,4, 4-tetramethyl cyclobutanedione into 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol through transfer hydrogenation and hydrogenation, thereby avoiding the occurrence of 2,2,4, 4-tetramethyl-trans-1, 3-cyclobutanediol and having the advantages of high catalytic efficiency, high product purity, less byproducts and the like.

Description

Reduction method of 2,2,4, 4-tetramethylcyclobutane
Technical Field
The invention relates to the technical field of chemistry, in particular to a reduction method of 2,2,4, 4-tetramethylcyclobutane.
Background
In the 2,2,4, 4-tetramethylcyclobutanedione reduction process, the common catalyst is easy to generate 2,2,4, 4-tetramethyl-trans-1, 3-cyclobutanediol in the process of reducing 2,2,4, 4-tetramethylcyclobutanedione into 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol through transfer hydrogenation and hydrogenation, and the purity of the product is influenced.
A feyieli (R.Noyori) hydrogenation catalyst refers to a chiral complex formed by coordination of a chiral diphosphine ligand BINAP and ruthenium (Ru) metal. Such catalysts can reduce dehydroamino acids, enamines, unsaturated carboxylic acids, ketoesters, and simple ketones. The contribution of feitelian causes to asymmetric hydrogenation reactions shared the nubel prize with charpleise in 2001. The class of [ Ru (II) - (BINAP) ] catalysts developed by Noyori et al can be largely classified according to the anion: [ Ru (OAC)2(BINAP) ], [ RuX2(BINAP) ] (or [ Ru (arene)) (BINAP)) ] X; X ═ Cl, Br or I) and [ RuCl2(BINAP) (diamine) ]. The first two of the three catalysts have poor stability, and the third catalyst has good stability when being stored in an inert gas atmosphere.
Based on this, the invention provides a 2,2,4, 4-tetramethylcyclobutanedione reduction method by utilizing a Ru-Binap system of Noyori, and no relevant report about the method exists in the market at present.
Disclosure of Invention
The invention aims to provide a method for reducing 2,2,4, 4-tetramethylcyclobutanedione, which utilizes a Ru-Binap system of Noyori to reduce 2,2,4, 4-tetramethylcyclobutanedione into 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol through transfer hydrogenation and hydrogenation, thereby avoiding the occurrence of 2,2,4, 4-tetramethyl-trans-1, 3-cyclobutanediol and solving the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of reducing 2,2,4, 4-tetramethylcyclobutanedione comprising the steps of:
s1: 580ml of 4.16mol/ml triethylamine is added into a 2000ml four-neck flask which is provided with a mechanical stirrer, a reflux condenser, an inert gas inlet pipe, a thermometer and a dropping funnel, and 194ml of formic acid with the concentration of 5.14mol/ml is slowly dropped into the flask after the flask is cooled to 4 ℃ by an ice bath;
s2: adding 0.8mol and 112g of 2,2,4, 4-tetramethylcyclobutanedione, 100ml of dry DMF and 0.204g and 0.321mmol of RuCl [ (S, S) -Tsdpen [ (p-cymene) at normal temperature, and stirring at 40 ℃ for 48 h;
s3: adding 600ml of water with the temperature of 0 ℃, uniformly stirring and filtering;
s4: the filter cake was washed 2 times with 200ml of water to give 110g of crude product, which was dissolved in 500g of methanol, and the insoluble portion was filtered off, cooled to 0 ℃ and filtered to give 85g of 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol, having a concentration of 98.5% ee.
Further, the catalyst in S2 further includes [ ru (oac)2(BINAP) ]; [ RuX2(BINAP) ] X ═ Cl, Br, or I; [ RuCl2(BINAP) (diamine) ].
Furthermore, 0.8mol and 112g of 2,2,4, 4-tetramethylcyclobutanedione are added into an autoclave, 600ml of methanol is added, the catalyst in S2 is added, a cover is covered, nitrogen is introduced, vacuumizing is performed, hydrogen is introduced, vacuumizing is performed, the pressure of hydrogen is 10MPa, the temperature is heated to 120 ℃, the reaction is performed for 24 hours, the raw materials are detected to be completely reacted, cooling and filtering are performed, 500ml of dichloromethane is added, washing is performed for 3 times, and spin-drying is performed to obtain 110g of pure product with the concentration of 98.2% ee.
Compared with the prior art, the invention has the beneficial effects that:
according to the reduction method of the 2,2,4, 4-tetramethylcyclobutanedione provided by the invention, the Ru-Binap system of Noyori is utilized to reduce the 2,2,4, 4-tetramethylcyclobutanedione into the 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol through transfer hydrogenation and hydrogenation, so that the occurrence of the 2,2,4, 4-tetramethyl-trans-1, 3-cyclobutanediol is avoided, and the reduction method has the advantages of high catalytic efficiency, high product purity, few byproducts and the like.
Drawings
FIG. 1 is a reaction scheme of a first embodiment of the present invention;
FIG. 2 is a reaction scheme of example two of the present invention;
FIG. 3 is a chemical structure diagram of RuCl [ (S, S) -Tsdpen [ (p-cymene) of the catalyst of the present invention;
FIG. 4 is a chemical structural diagram of a Ru-Binap system of the catalyst of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
referring to fig. 1, in an embodiment of the present invention, a method for reducing 2,2,4, 4-tetramethylcyclobutanedione is provided, which includes the following steps:
the first step is as follows: 580ml of 4.16mol/ml triethylamine is added into a 2000ml four-neck flask which is provided with a mechanical stirrer, a reflux condenser, an inert gas inlet pipe, a thermometer and a dropping funnel, and 194ml of formic acid with the concentration of 5.14mol/ml is slowly dropped into the flask after the flask is cooled to 4 ℃ by an ice bath;
the second step is that: adding 0.8mol and 112g of 2,2,4, 4-tetramethylcyclobutanedione, 100ml of dry DMF and 0.204g and 0.321mmol of RuCl [ (S, S) -Tsdpen [ (p-cymene) at normal temperature, and stirring at 40 ℃ for 48 h;
the third step: adding 600ml of water with the temperature of 0 ℃, uniformly stirring and filtering;
the fourth step: the filter cake was washed 2 times with 200ml of water to give 110g of crude product, which was dissolved in 500g of methanol, and the insoluble portion was filtered off, cooled to 0 ℃ and filtered to give 85g of 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol, having a concentration of 98.5% ee.
Referring to FIGS. 3-4, in the above examples, the catalyst further includes [ Ru (OAC)2(BINAP) ]; [ RuX2(BINAP) ] X ═ Cl, Br, or I; [ RuCl2(BINAP) (diamine) ];
among them, the [ ru (oac)2(BINAP) ] catalyst shows extremely high chiral induction ability and catalytic activity in asymmetric hydrogenation of enamides, unsaturated carboxylic acids, isopropyl alcohol and the like.
[ RuX2(BINAP) ] X ═ Cl, Br or I catalyst is almost ineffective in β -ketoester hydrogenation reaction, [ Ru (OAC)2(BINAP) ] while [ RuX2(BINAP) ] catalyst containing halide ions is very effective for the catalysis of the substrate, and in addition, the catalyst also shows very good catalytic activity and enantioselectivity for ketone substrates with α -position hydroxyl, alkyl, dialkylamino, halogen and other functional groups, in the asymmetric reduction of such carbonyl compounds, the hydrogen pressure is generally required to be in the range of 50-100atm, methanol or ethanol is used as solvent, the conversion number of the catalyst (the ratio of the substrate to the amount of the catalyst substance) can reach more than 2000, the ee value of the product is more than 98% for the hydrogenation of β -ketoester, the ee value of other substrates is more than 92%, and [ RuX2(BINAP) ] hydrogen is acted to form a monohydrogen complex under the action of ruthenium in the catalytic cycle, and the selectivity of the product is characterized in that the carbonyl ion is also on the carbon-Si-carbon surface of the carbonyl.
The preparation of RuCl2(BINAP) (diamine) ] catalyst is generally divided into two steps: BINAP is firstly coordinated with [ RuCl2(benzene) ]2 in DMF solution, then a corresponding catalyst is obtained by adding chiral diamine (diamine), the catalyst is a novel catalyst discovered by Noyori in 1995, the catalyst is very effective for asymmetric hydrogenation of simple ketone compounds, the conversion number (the ratio of the quantity of a substrate to the quantity of a catalyst substance) in hydrogenation of acetophenone can reach 2400000, various aromatic ketones, heterocyclic aromatic ketones, unsaturated ketones and the like can be efficiently and highly enantioselectively hydrogenated by taking isopropanol as a solvent in the presence of a base (such as potassium tert-butoxide), the ee value of the product is as high as 99%, and BINAP and chiral amine must be matched in configuration: the chiral induction is best when 3, 5-dimethyl substitution is carried out on the phenyl group connected with the phosphorus atom in BINAP ligand (Xyl-BINAP), and the chiral diamine ligand is mainly cyclohexanediamine (DACH), 1, 2-diphenyl ethylenediamine (DPEN) and 1, 1-di (4-methoxybenzene) -2-isopropyl-1, 2-ethylenediamine (DaiPEN), and the effect of the catalyst is best when (R) -Xyl-BINAP and (R) -DaiPEN or (S) -Xyl-BINAP and (S) -DaiPEN are combined.
Example two:
referring to fig. 2, another embodiment of the present invention: adding 0.8mol and 112g of 2,2,4, 4-tetramethylcyclobutanedione into an autoclave, adding 600ml of methanol, adding the catalyst in the first embodiment, covering a cover, introducing nitrogen, vacuumizing, introducing hydrogen, vacuumizing, heating to 120 ℃ under the hydrogen pressure, reacting for 24 hours, detecting that the raw materials are completely reacted, cooling, filtering, adding 500ml of dichloromethane, washing for 3 times, and spin-drying to obtain 110g of a pure product with the concentration of 98.2% ee.
In summary, the following steps: according to the reduction method of the 2,2,4, 4-tetramethylcyclobutanedione provided by the invention, the Ru-Binap system of Noyori is utilized to reduce the 2,2,4, 4-tetramethylcyclobutanedione into the 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol through transfer hydrogenation and hydrogenation, so that the occurrence of the 2,2,4, 4-tetramethyl-trans-1, 3-cyclobutanediol is avoided, and the reduction method has the advantages of high catalytic efficiency, high product purity, few byproducts and the like.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.

Claims (3)

1. A method for reducing 2,2,4, 4-tetramethylcyclobutane ketone is characterized by comprising the following steps:
s1: 580ml of 4.16mol/ml triethylamine is added into a 2000ml four-neck flask which is provided with a mechanical stirrer, a reflux condenser, an inert gas inlet pipe, a thermometer and a dropping funnel, and 194ml of formic acid with the concentration of 5.14mol/ml is slowly dropped into the flask after the flask is cooled to 4 ℃ by an ice bath;
s2: adding 0.8mol and 112g of 2,2,4, 4-tetramethylcyclobutanedione, 100ml of dry DMF and 0.204g and 0.321mmol of RuCl [ (S, S) -Tsdpen [ (p-cymene) at normal temperature, and stirring at 40 ℃ for 48 h;
s3: adding 600ml of water with the temperature of 0 ℃, uniformly stirring and filtering;
s4: the filter cake was washed 2 times with 200ml of water to give 110g of crude product, which was dissolved in 500g of methanol, and the insoluble portion was filtered off, cooled to 0 ℃ and filtered to give 85g of 2,2,4, 4-tetramethyl-cis-1, 3-cyclobutanediol, having a concentration of 98.5% ee.
2. The process for reducing 2,2,4, 4-tetramethylcyclobutanedione according to claim 1, wherein the catalyst in S2 further comprises [ Ru (OAC)2(BINAP) ]; [ RuX2(BINAP) ] X ═ Cl, Br, or I; [ RuCl2(BINAP) (diamine) ].
3. The reduction method of 2,2,4, 4-tetramethylcyclobutanedione as claimed in claim 1, wherein 0.8mol of 2,2,4, 4-tetramethylcyclobutanedione is added to an autoclave, 112g of methanol is added, 600ml of methanol is added, the catalyst in S2 is added, a lid is closed, nitrogen is introduced, vacuum is applied, hydrogen is introduced, vacuum is applied, the hydrogen pressure is 10MPa, the temperature is 120 ℃, the reaction is carried out for 24 hours, the reaction of raw materials is detected to be complete, cooling is carried out, filtration is carried out, 500ml of dichloromethane is added, washing is carried out for 3 times, and drying is carried out to obtain 110g of pure product with a concentration of 98.2% ee.
CN202010423832.XA 2020-05-19 2020-05-19 Reduction method of 2,2,4, 4-tetramethylcyclobutane Withdrawn CN111423307A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN112023919A (en) * 2020-07-30 2020-12-04 浙江恒澜科技有限公司 Catalyst, device and method for preparing high cis-trans ratio 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol

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WO2013135869A1 (en) * 2012-03-15 2013-09-19 Fundació Institut Català D'investigació Quimica Process for the preparation of optically active 1,2-di(furan-2-yl)ethane-1,2-diols and derivates thereof
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WO2013135869A1 (en) * 2012-03-15 2013-09-19 Fundació Institut Català D'investigació Quimica Process for the preparation of optically active 1,2-di(furan-2-yl)ethane-1,2-diols and derivates thereof
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BELA TOROK等: "Transformation of organic compounds in the presence of metal complexes VII*. Selective reduction of diketones by hydrosilylation in the presence of rhodium(I) complexes", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112023919A (en) * 2020-07-30 2020-12-04 浙江恒澜科技有限公司 Catalyst, device and method for preparing high cis-trans ratio 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol
CN112023919B (en) * 2020-07-30 2022-07-08 浙江恒逸石化研究院有限公司 Catalyst, device and method for preparing high cis-trans ratio 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol

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