CN115304465B - Green method for converting 1, 3-dithiane derivative into carbonyl compound - Google Patents

Green method for converting 1, 3-dithiane derivative into carbonyl compound Download PDF

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CN115304465B
CN115304465B CN202110492534.0A CN202110492534A CN115304465B CN 115304465 B CN115304465 B CN 115304465B CN 202110492534 A CN202110492534 A CN 202110492534A CN 115304465 B CN115304465 B CN 115304465B
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carbonyl compound
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赵国栋
雷海民
王亚欣
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Beijing University of Chinese Medicine
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Abstract

The invention provides a green method for converting a 1, 3-dithiane derivative into a carbonyl compound, belonging to the field of green organic chemistry. The method uses MBr x (M is Fe 3+ 、Ce 3+ 、Ce 4+ Etc., x is 3-4) is a catalyst, H 2 O 2 The deprotection reaction of thioacetal (ketone) is rapidly completed by in situ generation of active bromine (RBS) as a direct oxidant under neutral, open, room temperature conditions as the sole oxidant. Catalysts useful in the present invention (e.g., ceBr 3 、FeBr 3 Etc.), oxidant H 2 O 2 And solvents (such as ethanol, n-butanol, etc.) are inexpensive and readily available, and the reaction time is short and the strip is longThe method is mild in component, has wide functional group compatibility, high in product yield (75% -99%), simple in post-treatment and easy to operate, is a current very green, environment-friendly and safe method for deprotection of the mercaptal (ketone) into carbonyl compounds, and has wide application prospect.

Description

Green method for converting 1, 3-dithiane derivative into carbonyl compound
Technical Field
The invention belongs to the technical field of green chemistry and organic synthesis, and particularly relates to a green method for converting a 1, 3-dithiane derivative into a carbonyl compound.
Background
Carbonyl protection is often an essential step in many organic synthesis reactions, especially in the total synthesis of natural products and multifunctional organic compounds. Thioacetal (ketone) is a widely used carbonyl protecting group due to its ease of preparation and high stability under acidic and basic conditions.
Currently, there are many methods for deprotection of 1, 3-dithiane derivatives, for example, stoichiometric amounts or excess amounts of toxic reactants including mercury (II) and other heavy metal salts are available; in addition, there are methods using heterogeneous conditions, using various Fe (III) and Cu (II) salts, and other solvent-free methods, etc., but these methods generally require severe reaction conditions. The use of thioacetal (ketone) compounds in complex molecular synthesis is often hindered by the lack of mild, general removal methods. Traditionally, cleavage of thioacetals (ketones) is achieved mainly by oxidation means or by the action of mercury (II) salts, however, these methods often lead to competing side reactions in the presence of olefins, aromatic rings, groups susceptible to oxidation and acid sensitive functional groups and can cause a certain pollution to the environment.
Therefore, it is of great importance to develop a green, efficient, easy to handle and universally applicable method for deprotection of an aldol (ketone) acetal into a carbonyl compound.
Disclosure of Invention
The object of the present invention was to develop a versatile, green process for the conversion of 1, 3-dithiane derivatives to carbonyl compounds.
The invention adopts the technical scheme that:
a green process for converting 1, 3-dithiane derivatives to carbonyl compounds:
under neutral, open and room temperature conditions, MBr is used x (M is Fe 3+ 、Ce 3+ 、Ce 4+ Etc., x is 3-4) as catalyst, H 2 O 2 The reaction of the 1, 3-dithiane derivative to the carbonyl compound is completed in a short time as the sole oxidizing agent.
The reaction is carried out in a solvent, which may be methanol, ethanol, n-butanol, acetonitrile, tetrahydrofuran, diethyl ether, dichloromethane, dimethyl tetrahydrofuran, etc.
The reaction substrate is a 1, 3-dithiane derivative with different functional groups, wherein the functional groups can be different functional groups such as hydrogen groups, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, ester groups, alicyclic hydrocarbons and the like or different substituents such as furan, pyridine, thiophene, pyrrole and other heterocyclic rings, and can also be common protecting groups such as Ac, TBS, THP, bn, boc, TIPS and the like.
The reaction is carried out under the condition of a catalyst, wherein the catalyst is CeBr 3 、FeBr 3 、CeBr 4 Ce (NO) 3 ) 3 -KBr、CeCl 3 -KBr、Ce 2 (C 2 O 4 ) 3 -KBr、FeCl 3 -KBr、Fe(NO 3 ) 3 -KBr、Ce(SO 4 ) 2 Metals such as KBr (Ce 3+ 、Fe 3+ 、Ce 4+ ) And any one of combinations of bromides.
In specific operation, a scheme is provided: by reacting 1, 3-dithiane derivatives with catalysts, e.g. FeBr 3 、CeBr 3 Adding 0.01-0.2eq of ethanol into proper amount, stirring uniformly, and adding H into the stirring suspension 2 O 2 Aqueous solution (30 wt%,2-10 eq). The reaction mixture was stirred at room temperature for 5-40min. After completion of the reaction, diluted Na was used 2 S 2 O 3 The solution (0.1M) was quenched and extracted with ethyl acetate. The organic phase was collected and the aqueous phase was extracted 2-3 times with ethyl acetate. And (3) after the organic phases are combined, washing with water, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain the product.
The invention has the beneficial effects that:
compared with the prior art, the invention has the following advantages and effects:
the invention realizes the method of MBr under neutral condition for the first time x -H 2 O 2 In-situ formation of RBS catalyzes the reaction of 1, 3-dithiane derivative to carbonyl compound, and is one kind of amplified green method of eliminating carbonyl protecting group. Compared with the prior method for deprotection of mercaptal (ketone) into carbonyl compound,the method has the characteristics of easily available raw materials, low cost, quick reaction, wide substrate application range, simple route, easy operation, environmental friendliness and the like, and has more advantages than all the previous methods and good application prospect.
Drawings
FIGS. 1 and 2 are illustrations of example 1 1 H-NMR 13 C-NMR spectrum
FIGS. 3 and 4 are illustrations of example 2 1 H-NMR 13 C-NMR spectrum
FIGS. 5 and 6 are illustrations of example 3 1 H-NMR 13 C-NMR spectrum
FIGS. 7 and 8 are illustrations of example 4 1 H-NMR 13 C-NMR spectrum
FIGS. 9 and 10 are illustrations of example 5 1 H-NMR 13 C-NMR spectrum
FIGS. 11 and 12 are the examples 6 1 H-NMR 13 C-NMR spectrum
FIGS. 13 and 14 are examples 7 1 H-NMR 13 C-NMR spectrum
FIGS. 15 and 16 are the examples 8 1 H-NMR 13 C-NMR spectrum
FIGS. 17 and 18 are illustrations of example 9 1 H-NMR 13 C-NMR spectrum
FIGS. 19 and 20 are illustrations of embodiment 10 1 H-NMR 13 C-NMR spectrum
FIGS. 21 and 22 are illustrations of example 11 1 H-NMR 13 C-NMR spectrum
FIGS. 23 and 24 are illustrations of example 12 1 H-NMR 13 C-NMR spectrum
Detailed Description
The invention is described in detail below with reference to specific embodiments, but the scope of the invention is not limited thereto.
In the following examples 1 H-NMR 13 The C-NMR spectra were all determined at room temperature and recorded on a 400MHz spectrometer, 1 the H is set to be 400MHz, 13 c is 100MHz and the spectrometer is from Bruce.
Example 1
Ethanol (40 ml, 1 a) (4 mmol,1 g) was added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 1b (yield: 95%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ2.37(t，J＝7.5Hz，4H)，1.66-1.47(m，4H)，1.40-1.16(m，8H)，0.87(t，J＝7.1Hz，6H). 13 C-NMR(100MHz，CDCl 3 )δ211.82(s)，42.90(s)，31.58(s)，23.70(s)，22.59(s)，14.04(s).
example 2
Ethanol (40 ml, 2 a) (4 mmol,1 g) was added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 2b (yield: 87%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.46(s，1H)，8.03(dd，J＝8.6，1.7Hz，1H)，7.96(d，J＝8.0Hz，1H)，7.88(dd，J＝8.1，5.7Hz，2H)，7.66-7.51(m，2H)，2.72(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ198.20(s)，135.70(s)，134.61(s)，132.63(s)，130.30(s)，129.66(s)，128.55(d，J＝5.2Hz)，127.89(s)，126.88(s)，124.01(s)，26.79(s).
example 3
Ethanol 50ml and ethanol 3a (5 mmol,1.1 g) are sequentially added into a 100ml round bottom flask, uniformly stirred, and CeBr is sequentially added into the mixture of the two 3 (0.4mmol，0.152g)，H 2 O 2 Aqueous (30 wt%,15mmol,1.53 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 75 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 3b (yield: 92%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.70(dd，J＝3.8，1.1Hz，1H)，7.63(dd，J＝5.0，1.1Hz，1H)，7.13(dd，J＝4.9，3.8Hz，1H)，2.57(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ190.86(s)，144.74(s)，133.90(s)，132.58(s)，128.24(s)，27.08(s).
example 4
Ethanol 40ml and 4a (4 mmol,1.1 g) are added into a 100ml round bottom flask in turn, stirred evenly, and CeBr is added into the mixture of the two in turn 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase is collected and the organic phase is taken up,the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 4b (yield: 97%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.80(dd，J＝5.2，3.3Hz，1H)，7.63-7.55(m，1H)，7.48(dd，J＝10.5，4.7Hz，1H). 13 C-NMR(100MHz，CDCl 3 )δ196.84(s)，137.71(s)，132.52(s)，130.16(s)，128.38(s).
example 5
Ethanol 40ml and 5a (4 mmol,0.95 g) were added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 5b (yield: 81%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.14-7.98(m，1H)，7.46(td，J＝7.5，1.4Hz，1H)，7.39-7.10(m，2H)，2.96(t，J＝6.1Hz，2H)，2.84-2.55(m，2H)，2.14(dt，J＝12.6，6.4Hz，2H). 13 C-NMR(100MHz，CDCl 3 )δ198.48(s)，144.59(s)，133.49(s)，132.72(s)，128.87(s)，127.26(s)，126.72(s)，39.27(s)，29.81(s)，23.39(s).
example 6
Ethanol 40ml, 6a (4 mmol,0.96 g) were added sequentially to a 100ml round bottom flask, stirred well, and then a mixture of the two was addedSequentially adding CeBr 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 6b (yield: 78%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.13-7.83(m，2H)，7.11-6.68(m，2H)，3.87(s，3H)，2.55(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ196.91(s)，163.62(s)，130.72(s)，130.49(s)，113.81(s)，55.60(s)，26.47(s).
example 7
Ethanol (40 ml, 7 a) (4 mmol,1.1 g) was added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 7b (yield: 75%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.99(d，J＝8.7Hz，1H)，7.19(d，J＝8.7Hz，1H)，2.59(s，2H)，2.32(s，2H). 13 C-NMR(100MHz，CDCl 3 )δ196.90(s)，168.93(s)，154.43(s)，134.81(s)，130.02(s)，121.85(s)，26.66(s)，21.21(s).
example 8
Ethanol 30ml and 8a (3 mmol,0.95 g) were added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.24mmol，0.091g)，H 2 O 2 Aqueous (30 wt%,9mmol,0.92 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 45 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 8b (yield: 82%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ8.05-7.83(m，2H)，7.54-7.28(m，5H)，7.11-6.89(m，2H)，5.13(s，2H)，2.55(s，3H). 13 C-NMR(100MHz，CDCl 3 )δ196.83(s)，162.71(s)，136.28(s)，130.66(d，J＝6.8Hz)，128.79(s)，128.34(s)，127.56(s)，114.64(s)，70.22(s)，26.44(s).
example 9
Ethanol (40 ml, 9 a) (4 mmol,1.1 g) was added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed successively with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 9b (yield: 96%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ7.65(d，J＝7.3Hz，2H)，7.48(ddd，J＝8.9，8.4，4.0Hz，4H)，7.35-7.20(m，2H). 13 C-NMR(100MHz，CDCl 3 )δ194.04(s)，144.56(s)，134.80(s)，134.28(s)，129.20(s)，124.44(s)，120.43(s).
example 10
Ethanol (40 ml, 10 a) (4 mmol,1 g) was added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed sequentially with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 10b (yield: 89%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ10.11(s，1H)，8.27(s，1H)，7.90(ddd，J＝25.8，13.7，8.6Hz，4H)，7.68-7.43(m，2H). 13 C-NMR(100MHz，CDCl 3 )δ192.24(s)，136.45(s)，134.56(s)，134.12(s)，132.65(s)，129.55(s)，129.12(d，J＝4.0Hz)，128.10(s)，127.12(s)，122.75(s).
example 11
Ethanol (40 ml, 11 a) (4 mmol,1 g) was added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases are combined and washed with water, dried over anhydrous sodium sulfate and washed with waterFiltration and concentration under reduced pressure gave the objective product 11b (yield: 83%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ9.81(s，1H)，7.49-7.33(m，2H)，6.94(d，J＝8.2Hz，1H)，3.92(d，J＝10.7Hz，6H). 13 C-NMR(100MHz，CDCl 3 )δ190.96(s)，154.49(s)，149.61(s)，130.13(s)，126.94(s)，110.40(s)，108.88(s)，56.12(d，J＝19.1Hz).
example 12
Ethanol 40ml and 12a (4 mmol,0.95 g) were added sequentially to a 100ml round bottom flask, stirred well, and CeBr was then added sequentially to the mixture of the two 3 (0.32mmol，0.122g)，H 2 O 2 Aqueous (30 wt%,12mmol,1.23 ml) was stirred at room temperature for 10min. After the reaction is completed, na is used 2 S 2 O 3 The reaction was quenched with solution (0.1M, 60 mL) and extracted with ethyl acetate (100 mL). The organic phase was collected and the aqueous phase was extracted with ethyl acetate (2×50 mL). The organic phases were combined and washed sequentially with water, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give the desired product 12b (yield: 75%). Characterization data for this compound are as follows: 1 H-NMR(400MHz，CDCl 3 )δ9.80(s，1H)，7.88-7.50(m，2H)，6.85(d，J＝8.2Hz，1H)，4.66(t，J＝8.8Hz，2H)，3.24(t，J＝8.8Hz，2H). 13 C-NMR(100MHz，CDCl 3 )δ190.71(s)，165.70(s)，133.05(s)，130.46(s)，128.51(s)，125.96(s)，109.66(s)，72.48(s)，28.80(s).

Claims (6)

1. a green process for converting a 1, 3-dithiane derivative to a carbonyl compound, the process comprising: under the neutral, open and room temperature conditions, 1, 3-dithiane derivatives with different functional groups are used as reaction substrates, ceBr is used as a reaction substrate 3 As catalyst, H 2 O 2 The reaction of converting the 1, 3-dithiane derivative into carbonyl compound is completed in 5-40 min; reverse-rotationThe reaction is carried out in a solvent, wherein the reaction solvent is ethanol, and the 1, 3-dithiane derivatives are respectively as follows:
carbonyl compounds are respectively:
2. the method according to claim 1, characterized in that: catalyst CeBr 3 The molar ratio of the catalyst to the 1, 3-dithiane derivative is 0.01-0.2:1.
3. The method according to claim 1, characterized in that: h 2 O 2 The concentration is 3-30%, H 2 O 2 The molar ratio of the catalyst to the 1, 3-dithiane derivative is 2-10:1.
4. The method according to claim 1, characterized in that: the ratio of the 1, 3-dithiane derivative to the solvent is 1 mmol/10-20 mL.
5. The method according to claim 1, characterized in that: in the specific operation, the 1, 3-dithiane derivative and the catalyst are added into proper amount of solvent and stirred evenly, and then H is added into the stirred suspension 2 O 2 The reaction mixture is stirred and reacted for 5 to 40 minutes at room temperature to complete the reaction of converting the 1, 3-dithiane derivative into the carbonyl compound.
6. The method according to claim 1, characterized in that: after completion of the reaction, diluted Na was used 2 S 2 O 3 Quenching the solution, extracting with ethyl acetate, collecting organic phase, extracting the water phase with organic solvent for 2-3 times, mixingWashing the organic phase with water, drying with anhydrous sodium sulfate, filtering, and concentrating under reduced pressure to obtain carbonyl compound.
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