CN103319344A - 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon - Google Patents

1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon Download PDF

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CN103319344A
CN103319344A CN2013102247625A CN201310224762A CN103319344A CN 103319344 A CN103319344 A CN 103319344A CN 2013102247625 A CN2013102247625 A CN 2013102247625A CN 201310224762 A CN201310224762 A CN 201310224762A CN 103319344 A CN103319344 A CN 103319344A
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mesoporous carbon
sulfonation
cage modle
synthetic
diacetate esters
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CN103319344B (en
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李宝林
郑彦军
卢俊金
贾玉才
王伟
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Shaanxi Normal University
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Abstract

The invention relates to 1,1-diacetate synthesis catalyzed by sulfonated cage-type mesoporous carbon. The method is characterized in that aldehyde and acetic anhydride are placed in a reactor according to a molar ratio of 1:1-3; a sulfonated cage-type mesoporous carbon catalyst is added, wherein 5-20mg of the sulfonated cage-type mesoporous carbon catalyst is added to each mole of aldehyde; the materials are stirred under room temperature until a reaction is sufficiently carried out; ethyl acetate with a volume 20-30 times that of the reaction liquid is added; the catalyst is removed by filtering; a filtrate is washed three times by using a saturated NaHCO3 water solution, and once by using water; an organic phase is dried by using anhydrous Na2SO4; the solvent is removed by reduced-pressure distillation under a pressure of 0.09MPa, such that a crude product is obtained; and re-crystallization or column chromatographic separation is carried out, such that 1,1-diacetate is obtained. Compared with existing 1,1-diacetate synthesizing method, the method provided by the invention has the advantages of short reaction time, high yield, mild reaction condition, recyclable catalyst, and the like. The method can be used for synthesizing 1,1-diacetate.

Description

1 of sulfonation cage modle mesoporous carbon catalysis, the 1-diacetate esters is synthetic
Technical field
The invention belongs to acylal compounds technical field, be specifically related to 1,1-diacetate esters.
Background technology
1,1-diacetate esters belongs to the acylal compounds, and this compounds is the important intermediate of organic synthesis; By obtained by aromatic aldehyde 1, the acquisition nitrile compounds that the nucleophilic substitution reaction of 1-diacetate esters can high yield; By allyl aldehyde derive and come 1, the 1-diacetate esters under the catalysis of palladium by and multiple carbon containing or contain that single between oxygen affinity nuclear reagent replaces or two substitution reaction can be converted into multiple useful compound; 1,1-diacetate esters also is the substitute materials of carbonyl compound in the precursor of synthesis of acetyl oxygen base diolefine and the asymmetric synthesis; More noticeable is in recent years 1, and the 1-diacetate esters has become the important resultant of aldehyde radical selective protection in the organic synthesis.
1,1-diacetate esters is generated in the presence of an acidic catalyst by carbonyl compound and diacetyl oxide usually.The catalyzer of having used in this reaction has protonic acid so far, as sulfuric acid, and phosphoric acid, methylsulfonic acid, perchloric acid and Lewis acid are as BF 3, PCl 3, ZnCl 2, LiBF 4, ZrCl 4, FeCl 3, Zn (ClO 4) 26H 2O, RuCl 3XH 2O, SbCl 3Deng two big classes.In addition, also have some heterogeneous catalyst, as SiO 2, zeolite, montmorillonite, macroporous resin, AlPW 12O 40And H 6P 2W 18O 6224H 2O is also as this catalyst for reaction.Yet, more than the main drawback of these catalyzer are strong acid conditions, need the long reaction times, productive rate and selectivity are lower, product is difficult the separation, or price is higher, recovery utilization rate is low etc.
Summary of the invention
It is above-mentioned 1 that technical problem to be solved by this invention is to overcome, existing shortcoming during the 1-diacetate esters is synthetic, provide that a kind of technology is simple, yield is high, purity is good, the sulfonation cage modle mesoporous carbon catalysis of the recyclable usefulness again of catalyzer 1, the 1-diacetate esters is synthetic.
Solving the problems of the technologies described above the technical scheme that adopts is made up of following step:
Aldehyde and diacetyl oxide are placed reactor by 1:1～3 mol ratios, add sulfonation cage modle gold/mesoporous carbon catalyst, every mole of aldehyde adds 5～20mg sulfonation cage modle gold/mesoporous carbon catalyst, is stirred under the room temperature to react completely; The ethyl acetate that adds 20～30 times of reaction solution volumes, the elimination catalyzer, filtrate is with saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, the 0.09MPa decompression steams solvent and obtains crude product, separates through recrystallization or column chromatography, obtains 1,1-diacetate esters.
Chemical equation is as follows:
R is alkyl or aryl in the formula.
In the proportioning raw materials of the present invention, aldehyde and diacetyl oxide the best place reactor by the 1:2.5 mol ratio, add sulfonation cage modle gold/mesoporous carbon catalyst, and catalyst consumption is the sulfonation cage modle mesoporous carbon that every mole of aldehyde is used 15mg, is stirred under the room temperature to react completely; The ethyl acetate that adds 20～30 times of reaction solution volumes, the elimination catalyzer, filtrate is with saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, the 0.09MPa decompression steams solvent, gets crude product, and recrystallization or column chromatography are separated, and get 1,1-diacetate esters.
Alkyl of the present invention is straight chain or the alkyl with side chain, and its carbonatoms is 1～10.
Aryl of the present invention is substituted aryl or unsubstituting aromatic yl.
Substituted aryl of the present invention is C 1-4Alkyl, C 1-4Alkane-oxyl, halogenated methyl, halogen, nitro, C 2-4Alkylene, C 2-4The alkynes base in any one; Substituent number is 1～3.
Substituted aryl of the present invention is preferably C 1-4Alkyl, C 1-4In alkane-oxyl, halogenated methyl, halogen, the nitro any one.
Aryl of the present invention is benzene series aryl or heterocyclic aryl or fused ring aryl.
Because the present invention has adopted sulfonation cage modle gold/mesoporous carbon catalyst, at ambient temperature, the reaction times is 5～12 minutes, and yield is 89%～98%.The present invention and existing 1, the synthetic method of 1-diacetate esters is compared, have the reaction times short, yield is high, reaction conditions is gentle, the recyclable advantage such as use again of catalyzer, can be used for synthetic 1,1-diacetate esters.
Embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Catalyst system therefor sulfonation cage modle mesoporous carbon press document (Pei Lin, Baolin Li, Jiangtao Li, et al.Catal Lett, 2011,141 (3): 459-466) method preparation, concrete grammar is as follows:
Be structure directing agent with triblock copolymer (F127), tetraethoxy is the silicon source, and is synthetic through 150 ℃ of hydro-thermals, and calcining is removed structure directing agent and obtained mesoporous silicon oxide in the retort furnace.Be the silicon template with silicon-dioxide, sucrose is carbon source, pours into sucrose twice in the silicon template repeatedly, and through thermopolymerization, forming is situated between sees phase, at N 2Carbonization in the atmosphere is removed the silicon template with hydrofluoric acid dips, obtains the cage modle mesoporous carbon, and specific surface area is 1368m 2/ g; Be solvent with water, 80 ℃ of stirrings, surface-functionalized with the aryl radical pair mesoporous carbon that Isopentyl nitrite and Sulphanilic Acid reaction produce, obtain to have sulfonic cage modle mesoporous carbon.Be alkaline reagents with NaOH, the sour density that records its support by potentiometric titration is 1.53 ± 0.09mmol/g, and specific surface area is 780m 2/ g.
It is the cage modle meso-hole structure that catalyzer characterizes its structure through transmission electron microscope, X-ray diffraction, physical adsorption and method of infrared spectrophotometry; The sulfonic group density of catalyst surface support is measured as 1.53 ± 0.09mmol/g through potentiometric titration.
The used instrument of structural characterization is: Bruker AVANCE400 superconduction fourier numeralization nuclear magnetic resonance spectrometer; The micro-molten some determinator of X-6 (Tyke, Beijing Instr Ltd.), GCMS-QP2010 instrument (day island proper Tianjin company).
Embodiment 1
Be example with synthetic 1,1-diacetoxy-1-(2-trifluoromethyl) methane, the structural formula of 1,1-diacetoxy-1-(2-trifluoromethyl) methane is:
Figure BDA00003310974000031
Its synthetic method is as follows:
Add 2-trifluoromethylated benzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to fully with TLC, adds ethyl acetate 20～30mL, the saturated NaHCO of filtering catalyst, filtrate 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product separates (eluent is that the volume ratio of ethyl acetate and sherwood oil is 1:8) through column chromatography and obtains pure products, and productive rate is: 96%, m.p.71-72 ℃; 1H NMR (400MHz, CDCl 3) δ 8.02 (s, 1H), 7.78 (d, J=7.8Hz, 1H), 7.71 (d, J=7.8Hz, 1H), 7.63 (t, J=7.6Hz, 1H), 7.53 (t, J=7.6Hz, 1H), 2.13 (s, 6H) .MS (EI): 276 (M +), 258,233,217,173,155,145,127,103,75,43.
2-trifluoromethylated benzaldehyde in the present embodiment can be replaced with equimolar 2-trichloromethyl phenyl aldehyde, synthesizes into 1,1-diacetoxy-1-(2-trichloromethyl phenyl) methane; The 2-trifluoromethylated benzaldehyde can be replaced with equimolar 2-trisbromomethyl phenyl aldehyde, synthesizes into 1,1-diacetoxy-1-(2-trisbromomethyl phenyl) methane.
Embodiment 2
Be example with synthetic 1,1-diacetoxy-1-(2-bromo-4,5-Dimethoxyphenyl) methane, the structural formula of 1,1-diacetoxy-1-(2-bromo-4,5-Dimethoxyphenyl) methane is:
Figure BDA00003310974000032
Its synthetic method is as follows:
Add 2-bromo-4,5-dimethoxy benzaldehyde 2mmol, diacetyl oxide 5mmol in the single port bottle of 25mL, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC, add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product separates (eluent is that the volume ratio of ethyl acetate and sherwood oil is 1:5) through column chromatography and obtains pure products, and productive rate is: 97%, m.p.84-85 ℃; 1H NMR (400MHz, CDCl3) δ 7.87 (s, 1H), 7.04 (d, J=4.2Hz, 2H), 3.91 (s, 3H), 3.88 (s, 3H), 2.14 (s, 6H) .MS (EI): 348 ([M+2] +), 346 (M +), 246,244,225,183,138,94,79,51,43.
Embodiment 3
Be example with synthetic 1,1-diacetoxy-1-(phenyl) methane, the structural formula of 1,1-diacetoxy-1-(phenyl) methane is:
Figure BDA00003310974000041
Its synthetic method is as follows:
Add phenyl aldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 96%, m.p.65-66 ℃, and MS (EI): 238 (M +), 179,153,135,107,92,77,43.
Embodiment 4
Be example with synthetic 1,1-diacetoxy-1-(3-aminomethyl phenyl) methane, the structural formula of 1,1-diacetoxy-1-(3-aminomethyl phenyl) methane is:
Figure BDA00003310974000042
Its synthetic method is as follows:
Add 3-tolyl aldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to fully with TLC, adds ethyl acetate 20～30mL, the saturated NaHCO of filtering catalyst, filtrate 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain pure products, and productive rate is: 94%, MS (EI): 222 (M +), 180,163,137,119,91,77,65,51,43.
The 3-tolyl aldehyde of present embodiment also available equimolar 3-butylbenzene formaldehyde is replaced, and synthesizes into 1,1-diacetoxy-1-(3-butyl phenyl) methane; The 3-tolyl aldehyde is yet replaced with equimolar 3-propylbenzene formaldehyde, synthesizes into 1,1-diacetoxy-1-(3-propyl group phenyl) methane.
Embodiment 5
Be example with synthetic 1,1-diacetoxy-1-(4-aminomethyl phenyl) methane, the structural formula of 1,1-diacetoxy-1-(4-aminomethyl phenyl) methane is:
Figure BDA00003310974000051
Its synthetic method is as follows:
Add 4-tolyl aldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 8 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 93%, m.p.81 ℃, and MS (EI): 222 (M +), 179,163,137,119,91,77,65,51,43.
The 4-tolyl aldehyde of present embodiment also available equimolar 4-butylbenzene formaldehyde is replaced, and synthesizes into 1,1-diacetoxy-1-(4-butyl phenyl) methane; The 4-tolyl aldehyde is yet replaced with equimolar 4-propylbenzene formaldehyde, synthesizes into 1,1-diacetoxy-1-(4-propyl group phenyl) methane.
Embodiment 6
Be example with synthetic 1,1-diacetoxy-1-(2-p-methoxy-phenyl) methane, the structural formula of 1,1-diacetoxy-1-(2-p-methoxy-phenyl) methane is:
Figure BDA00003310974000052
Its synthetic method is as follows:
Add 2-methoxybenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 12 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 91%, m.p.74-75 ℃, and MS (EI): 238 (M +), 179,153,135,118,107,104,92,77,65,51,43.
The 2-methoxybenzaldehyde of present embodiment also available equimolar 2-butyl phenyl ether formaldehyde is replaced, and synthesizes into 1,1-diacetoxy-1-(2-butoxy phenyl) methane; The 2-methoxybenzaldehyde is available equimolar 2-propoxy-phenyl aldehyde also, synthesizes into 1,1-diacetoxy-1-(2-propoxy-phenyl) methane.
Embodiment 7
Be example with synthetic 1,1-diacetoxy-1-(4-p-methoxy-phenyl) methane, the structural formula of 1,1-diacetoxy-1-(4-p-methoxy-phenyl) methane is:
Figure BDA00003310974000061
Its synthetic method is as follows:
Add 4-methoxybenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 97%, m.p.65-66 ℃, and MS (EI): 238 (M +), 179,153,135,107,92,77,43.
The 4-methoxybenzaldehyde of present embodiment also available equimolar 4-butyl phenyl ether formaldehyde is replaced, and synthesizes into 1,1-diacetoxy-1-(4-butoxy phenyl) methane; The 4-methoxybenzaldehyde is available equimolar 4-propoxy-phenyl aldehyde also, synthesizes into 1,1-diacetoxy-1-(4-propoxy-phenyl) methane.
Embodiment 8
Be example with synthetic 1,1-diacetoxy-1-(3,4-Dimethoxyphenyl) methane, the structural formula of 1,1-diacetoxy-1-(3,4-Dimethoxyphenyl) methane is:
Figure BDA00003310974000062
Its synthetic method is as follows:
Add 3,4-dimethoxy benzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain pure products, and productive rate is: 95%, m.p.66-67 ℃, and MS (EI): 268 (M +), 166,151,139,95,77,65,43.
In the present embodiment 3, the 4-dimethoxy benzaldehyde can be with equimolar 3, and 4-dibutoxy phenyl aldehyde is replaced, and synthesizes into 1,1-diacetoxy-1-(3,4-dibutoxy phenyl) methane; 3,4-dimethoxy benzaldehyde is also available equimolar 3, and 4-dipropoxy phenyl aldehyde is replaced, and synthesizes into 1,1-diacetoxy-1-(3,4-dipropoxy phenyl) methane.
Embodiment 9
Be example with synthetic 1,1-diacetoxy-1-(2-nitrophenyl) methane, the structural formula of 1,1-diacetoxy-1-(2-nitrophenyl) methane is:
Its synthetic method is as follows:
Add 2-nitrobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 10 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 89%, m.p.85-86 ℃, and MS (EI): 207 (M +), 194,151,121,93,64,43.
Embodiment 10
Be example with synthetic 1,1-diacetoxy-1-(3-nitrophenyl) methane, the structural formula of 1,1-diacetoxy-1-(3-nitrophenyl) methane is:
Its synthetic method is as follows:
Add 3-nitrobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 8 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 94%, m.p.65-66 ℃, and MS (EI): 210 (M +), 194,151,134,105,77,51,43.
Embodiment 11
Be example with synthetic 1,1-diacetoxy-1-(4-nitrophenyl) methane, the structural formula of 1,1-diacetoxy-1-(4-nitrophenyl) methane is:
Its synthetic method is as follows:
Add 4-nitrobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 94%, m.p.125-126 ℃, and MS (EI): 210 (M +), 194,151,134,105,77,51,43.
Embodiment 12
Be example with synthetic 1,1-diacetoxy-1-(2-fluorophenyl) methane, the structural formula of 1,1-diacetoxy-1-(2-fluorophenyl) methane is:
Figure BDA00003310974000082
Its synthetic method is as follows:
Add 2-fluorobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain pure products, and productive rate is: 98%, m.p.26-27 ℃, and MS (EI): 226 (M +), 183,167,123,95,75,43.
Embodiment 13
Be example with synthetic 1,1-diacetoxy-1-(4-fluorophenyl) methane, the structural formula of 1,1-diacetoxy-1-(4-fluorophenyl) methane is:
Figure BDA00003310974000083
Its synthetic method is as follows:
Add 4-fluorobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 92%, m.p.50-51 ℃, and MS (EI): 226 (M +), 183,167,123,95,75,43.
Embodiment 14
Be example with synthetic 1,1-diacetoxy-1-(3-chloro-phenyl-) methane, the structural formula of 1,1-diacetoxy-1-(3-chloro-phenyl-) methane is:
Figure BDA00003310974000091
Its synthetic method is as follows:
Add 3-chlorobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon (30mg), stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain pure products, and productive rate is: 97%, m.p.66 ℃, and MS (EI): 242 (M +), 199,140,139,111,77,75,51,43.
Embodiment 15
Be example with synthetic 1,1-diacetoxy-1-(4-chloro-phenyl-) methane, the structural formula of 1,1-diacetoxy-1-(4-chloro-phenyl-) methane is:
Figure BDA00003310974000092
Its synthetic method is as follows:
Add 4-chlorobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 7 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain pure products, and productive rate is: 98%, m.p.73-74 ℃, and MS (EI): 242 (M +), 199,141,139,111,77,75,43.
Embodiment 16
Be example with synthetic 1,1-diacetoxy-1-(2,4 dichloro benzene base) methane, the structural formula of 1,1-diacetoxy-1-(2,4 dichloro benzene base) methane is:
Figure BDA00003310974000093
Its synthetic method is as follows:
Add 2,4 dichloro benzene formaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product obtains pure products with ethyl alcohol recrystallization, and productive rate is: 91%, m.p.98-99 ℃, and MS (EI): 278 ([M+2] +), 276 (M +), 241,199,173,175,145,111,75,43.
Embodiment 17
Be example with synthetic 1,1-diacetoxy-1-(4-bromophenyl) methane, the structural formula of 1,1-diacetoxy-1-(4-bromophenyl) methane is:
Its synthetic method is as follows:
Add 4-bromobenzaldehyde 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 8 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.The crude product normal hexane: ethanol 1:10 recrystallization obtains pure products, and productive rate is: 97%, m.p.89-90 ℃, and MS (EI): 286 ([M+2] +), 288 (M +), 245,185,183,157,155,77,50,43.
Embodiment 18
Be example with synthetic 1,1-diacetoxy pentane, the structural formula of 1,1-diacetoxy pentane is:
Its synthetic method is as follows:
Add valeral 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with GC-MS.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain pure products, and productive rate is: 93%, 188 (M +), 131,129,103,100,85,69,57,43.
Embodiment 19
Be example with synthetic 1,1-diacetoxy-1-(furyl) methane, the structural formula of 1,1-diacetoxy-1-(furyl) methane is:
Figure BDA00003310974000111
Its synthetic method is as follows:
Add furtural 2mmol in the single port bottle of 25mL, diacetyl oxide 5mmol, sulfonation cage modle mesoporous carbon 30mg, stirring reaction is 5 minutes under the room temperature solvent-free condition, follows the tracks of reaction to complete with TLC.Add ethyl acetate 20～30mL, filtering catalyst, filtrate is used saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, vacuum rotary steam go out solvent and obtain crude product.Crude product separates (eluent is that the volume ratio of ethyl acetate and sherwood oil is 1:9) with column chromatography and obtains pure products, and productive rate is: 90%, m.p.51 ℃, and MS (EI): 198 (M +), 155,139,97,95,53.
Embodiment 20
At above embodiment 1～19, aldehyde and diacetyl oxide are placed reactor by the 1:1 mol ratio, add sulfonation cage modle gold/mesoporous carbon catalyst, sulfonation cage modle gold/mesoporous carbon catalyst add-on is identical with embodiment 1, is stirred under the room temperature to react completely.Other steps are identical with embodiment 1, are prepared into 1,1-diacetate esters.
Embodiment 21
At above embodiment 1～19, aldehyde and diacetyl oxide are placed reactor by the 1:3 mol ratio, add sulfonation cage modle gold/mesoporous carbon catalyst, sulfonation cage modle gold/mesoporous carbon catalyst add-on is identical with embodiment 1, is stirred under the room temperature to react completely.Other steps are identical with embodiment 1, are prepared into 1,1-diacetate esters.

Claims (7)

1. 1 of sulfonation cage modle mesoporous carbon catalysis, the 1-diacetate esters is synthetic, it is characterized in that: aldehyde and diacetyl oxide are placed reactor by 1:1～3 mol ratios, add sulfonation cage modle gold/mesoporous carbon catalyst, every mole of aldehyde adds 5～20mg sulfonation cage modle gold/mesoporous carbon catalyst, is stirred under the room temperature to react completely; The ethyl acetate that adds 20～30 times of reaction solution volumes, the elimination catalyzer, filtrate is with saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, the 0.09MPa decompression steams solvent and obtains crude product, separates through recrystallization or column chromatography, obtains 1,1-diacetate esters, and reaction formula is as follows:
Figure DEST_PATH_FDA00003538070500011
R is alkyl or aryl in the formula.
2. 1 of sulfonation cage modle mesoporous carbon according to claim 1 catalysis, the 1-diacetate esters is synthetic, it is characterized in that: aldehyde and diacetyl oxide are placed reactor by the 1:2.5 mol ratio, add sulfonation cage modle gold/mesoporous carbon catalyst, catalyst consumption is the sulfonation cage modle mesoporous carbon that every mole of aldehyde is used 15mg, is stirred under the room temperature to react completely; The ethyl acetate that adds 20～30 times of reaction solution volumes, the elimination catalyzer, filtrate is with saturated NaHCO 3Solution washing 3 times is washed the organic phase anhydrous Na 1 time 2SO 4Drying, the 0.09MPa decompression steams solvent, gets crude product, and recrystallization or column chromatography are separated, and get 1,1-diacetate esters.
3. 1 of sulfonation cage modle mesoporous carbon according to claim 1 catalysis, the 1-diacetate esters is synthetic, and it is characterized in that: described alkyl is straight chain or the alkyl with side chain, and its carbonatoms is 1～10.
4. 1 of sulfonation cage modle mesoporous carbon according to claim 1 catalysis, the 1-diacetate esters is synthetic, and it is characterized in that: described aryl is substituted aryl or unsubstituting aromatic yl.
5. 1 of sulfonation cage modle mesoporous carbon according to claim 4 catalysis, the 1-diacetate esters is synthetic, and it is characterized in that: described substituted aryl is C 1-4Alkyl, C 1-4Alkane-oxyl, halogenated methyl, halogen, nitro, C 2-4Alkylene, C 2-4The alkynes base in any one; Substituent number is 1～3.
6. 1 of sulfonation cage modle mesoporous carbon according to claim 4 catalysis, the 1-diacetate esters is synthetic, and it is characterized in that: described substituted aryl is C 1-4Alkyl, C 1-4In alkane-oxyl, halogenated methyl, halogen, the nitro any one.
7. according to 1 of sulfonation cage modle mesoporous carbon according to claim 1 catalysis, the 1-diacetate esters is synthetic, and it is characterized in that: described aryl is benzene series aryl or heterocyclic aryl or fused ring aryl.
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CN104356175A (en) * 2014-11-24 2015-02-18 苏州乔纳森新材料科技有限公司 Method for preparing sucralose-6-acetate
CN112745211A (en) * 2021-01-21 2021-05-04 上海应用技术大学 Preparation method of isononanoic acid

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* Cited by examiner, † Cited by third party
Title
RAZIEH FAZAELI 等: "从醛无溶剂制备1,1-二乙酸酯的催化剂Cu3/2PMo12O40/ SiO2", 《催化学报》 *
吝佩: "磺化介孔碳材料的制备及其应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104356175A (en) * 2014-11-24 2015-02-18 苏州乔纳森新材料科技有限公司 Method for preparing sucralose-6-acetate
CN112745211A (en) * 2021-01-21 2021-05-04 上海应用技术大学 Preparation method of isononanoic acid
CN112745211B (en) * 2021-01-21 2022-10-14 上海应用技术大学 Preparation method of isononanoic acid

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