CN108395369A - A method of with graphene oxide-titanium sulfate nano-complex it is catalyst preparation aromatic aldehyde - Google Patents
A method of with graphene oxide-titanium sulfate nano-complex it is catalyst preparation aromatic aldehyde Download PDFInfo
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- CN108395369A CN108395369A CN201710068423.0A CN201710068423A CN108395369A CN 108395369 A CN108395369 A CN 108395369A CN 201710068423 A CN201710068423 A CN 201710068423A CN 108395369 A CN108395369 A CN 108395369A
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- aromatic aldehyde
- benzylalcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/294—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with hydrogen peroxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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Abstract
The invention discloses a kind of methods preparing aromatic aldehyde with graphene oxide titanium sulfate nano-complex (GO Ti), belong to fine chemical product preparing technical field.The present invention is using different structure fragrance benzylalcohol as reaction substrate, tetrahydrofuran etc. is used as solvent, hydrogen peroxide solution is as oxidant, oxidation reaction is carried out under the effect of GO Ti nano-complex catalysts, reaction temperature is 50 70 DEG C, reaction time is 3 12 hours, after reaction through column chromatography or the isolated aromatic aldehyde of vacuum distillation.The synthetic method of the present invention is simple, and solvent for use is recyclable, can also be aoxidized in the presence of solvent-free, and easy to operate, reaction condition is mild, and high financial profit is environmentally safe.Catalyst recycling still keeps very high conversion ratio and selectivity 10 times.
Description
Technical field：
The invention belongs to technical field of organic synthesis, and in particular to a kind of to use graphene oxide-titanium sulfate nano-complex
The method that aromatic aldehyde is synthesized by fragrant benzylalcohol for catalyst.
Background technology：
Aromatic aldehyde is widely used in medicine, fuel, fragrance, pesticide and material etc. as a kind of important industrial chemicals
In a variety of industrial circles.The open method for preparing aromatic aldehyde includes at present：Chlorinolysis, formic acid esters reduction method and direct oxidation
Aromatic compounds etc..But traditional preparation method technological process is long and final production yield is low；In addition it is needed in preparation engineering
The strong corrosives reagent such as a large amount of organic base is consumed, while generating a large amount of chlorine.Not only equipment is caused greatly to corrode, together
Shi Yanchong pollutes environment.Since the seventies in last century, load type metal catalyst starts widely to be studied and has obtained pole
Big application.But some catalyst itself have certain solubility in organic solvent, while cannot fix metal well,
Repeatedly different degrees of loss is had after cycle.
Patent CN104557786 is prepared for a kind of SiO2- CoO meets the method that gas phase gel prepares benzaldehyde, but should
Gel process for preparing is complicated.Patent CN104693002 directly obtains benzaldehyde using toluene oxidation, but this method uses oxygen
Oxidant is made, conversion ratio is very low, and toluene conversion is up to 51%, benzaldehyde selectively up to 91%.Patent
The method for preparing benzaldehyde with various metals continuous catalysis ozone oxidation cinnamic acid has been invented in CN104710295A.But this method
The problems such as needing the devices such as ozone generator, existing simultaneously environmental pollution.
Invention content：
In view of the deficiencies of the prior art, the present invention provides one kind using graphene oxide as catalyst carrier, with Ti (SO4)2
Stable nano-complex is formed, using the hydrogen peroxide of cheap environmental protection as oxidant high conversion and highly selective oxidation system
Standby aromatic aldehyde.
The present invention is achieved through the following technical solutions：
Reaction raw materials fragrance benzylalcohol is dissolved in organic reagent, homemade graphene oxide-loaded titanium sulfate (GO-Ti is added
Compound), and it is heated to 50-70 DEG C, 10~70% aqueous hydrogen peroxide solutions are then added and react 3-12 hours, pass through after reaction
It crosses column chromatography or vacuum distillation obtains product aromatic aldehyde.
Specifically, aromatic aldehyde is made by the steps in the present invention：
(1) 1~10%Ti will be contained4+GO-Ti compounds and fragrant benzylalcohol be distributed in organic solvent, it is used organic molten
Agent volume is fragrance benzylalcohol quality 5-20 (w/v) times, preferably 10-15 times；
Or directly GO-Ti is distributed in liquid aromatic benzylalcohol reactant, GO-Ti mass is the 1- of reactant quality
80%, preferably 10-50%.
(2) acquired solution in step (1) is preheating to 30-100 DEG C, preferably 50-70 DEG C in temperature constant magnetic stirring oil bath.
Mixing speed 1000-2000r/min.
(3) 1~4 times of 10~50% hydrogenperoxide steam generator of amount is directly added into solution described in step (2), preferably 2-3
30% hydrogenperoxide steam generator of amount again.
(4) solution described in step (3) reacts 3~12h, preferably 4~10h at 50-70 DEG C.
(5) Filtration of catalyst, merging filtrate after being washed 2-3 times with organic solvent concentrate, through silica gel after reaction
Column chromatography or vacuum distillation obtain final product aromatic aldehyde.
(6) it can be recycled again according to above-mentioned oxidation step after the catalyst drying organic solvent recycled in step (5).
Wherein, such as (I), (II), (III) or (IV) is shown for the fragrant benzylalcohol general structure described in step (1).
In logical formula (I), (II), (III), (IV), m, n are substituent group number, m=0,1,2,3,4；N=0,1,2,3,4,
5。
R, R ' can be hydrogen, halogen, nitro, C1-C5Linear or branched alkyl group.
Preferably, R, R ' can be F, Cl, Br.C1-C5Linear or branched alkyl group can be methyl, ethyl, isopropyl.
In step (1), organic solvent used includes methanol, ethyl alcohol, isopropanol, the tert-butyl alcohol, tetrahydrofuran, acetone, acetonitrile,
N,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane.If reaction raw materials and product are all liquid, can not also use any organic
Solvent.
GO-Ti compounds described in step (1) are graphene oxide-loaded titanium sulfate, and titanium sulfate quality is graphite oxide
The 1-10% of alkene quality.
Preparation method of the present invention is simple, high conversion rate, high selectivity, and catalyst may be reused.
Specific implementation mode：
HPLC conditions：
Mobile phase:Acetonitrile:Water=1:4 (0.4% triethylamines of addition), flow velocity=1.0ml/min
Embodiment 1
The GO-Ti of 0.72g (0.006mol) benzyl alcohols and 0.4g is dispersed in 10ml tetrahydrofuran solutions and in oil bath
Under be heated to 70 DEG C, 30% aqueous hydrogen peroxide solution of 2.26g (0.02mol) is slowly added in tetrahydrofuran, keeps the temperature
6h is reacted, phenmethylol conversion ratio 90.3%, benzaldehyde selectivity 99% are detected through HPLC.Filter is concentrated after Filtration of catalyst
Liquid obtains benzaldehyde 0.63g, yield after pillar layer separation：88.7%.1NMR(DMSO-d6):7.61 (m, 2H), 7.70 (m,
1H), 7.85 (m, 2H), 10.12 (s, 1H).EI-MS m/z:106[M]+。
Embodiment 2
According to method described in embodiment 1, solvent is changed to methanol, temperature is changed to 50 DEG C, and hydrogen peroxide is changed to 1.2 times of amounts,
Other conditions are constant.After reaction 3h phenmethylol conversion ratio 74.3%, benzaldehyde selectivity 98.9% are detected by HPLC.According to reality
It applies last handling process described in example 1 and obtains benzaldehyde 0.43g, yield 60.6%.
Embodiment 3
According to method described in embodiment 1, solvent is changed to acetonitrile, temperature is changed to 70 DEG C, and hydrogen peroxide is changed to 2.0 times of amounts,
Other conditions are constant.After reaction 5h phenmethylol conversion ratio 68.1%, benzaldehyde selectivity 99% are detected by HPLC.According to implementation
Last handling process described in example 1 obtains benzaldehyde 0.38g, yield：53.5%.
Embodiment 4
GO-Ti compounds 2.0g is scattered in 100g (0.925mol) benzyl alcohol, 70 DEG C are preheating under oil bath, is slowly added
Enter 30% hydrogen peroxide of 314.5g (2.775mol), reacts 12h.Reaction solution detects phenmethylol conversion ratio 88%, benzene first through HPLC
Aldehyde selectivity 98.4%.Merging filtrate after Filtration of catalyst dichloromethane 10mlX2 washing catalysts.It is evaporated under reduced pressure to
To benzaldehyde 82.0g, yield 83.6%.
Embodiment 5
According to method described in embodiment 1, temperature is 70 DEG C, and 10% hydrogen peroxide of 6.8g (0.02mol), other conditions are not
Become.After reaction 8h phenmethylol conversion ratio 70.3%, benzaldehyde selectivity 98% are detected by HPLC.Described in embodiment 1
Last handling process obtains benzaldehyde 0.43g, yield 60.6%.
Embodiment 6
According to method described in embodiment 1, temperature is 70 DEG C, and 20% hydrogen peroxide of 3.4g (0.02mol), other conditions are not
Become.After reaction 8h phenmethylol conversion ratio 82.3%, benzaldehyde selectivity 98.4% are detected by HPLC.According to institute in embodiment 1
It states last handling process and obtains benzaldehyde 0.56g, yield 78.9%.
Embodiment 7
According to method described in embodiment 1, temperature is 70 DEG C, and 50% hydrogen peroxide of 1.4g (0.02mol), other conditions are not
Become.After reaction 8h phenmethylol conversion ratio 91.3%, benzaldehyde selectivity 96.5% are detected by HPLC.According to institute in embodiment 1
It states last handling process and obtains benzaldehyde 0.58g, yield 81.7%.
Embodiment 8
The recycling of catalyst reuses
By catalyst (GO-Ti) recycling in embodiment 1, the experimentation of circulating repetition embodiment 1 after drying, 10
It is secondary.It is 89-91% that HPLC, which detects phenmethylol conversion ratio, and benzaldehyde is selectively 98-99.1%.
The preparation of 9 3,5- dimethylbenzaldehydes of embodiment
The GO-Ti of the 3,5- dimethylphenylcarbinols of 0.91g (0.0067mol) and 0.4g is scattered in 10ml tetrahydrofurans
In, and 70 DEG C are heated under oil bath, the 30wt% aqueous hydrogen peroxide solutions of 1.89g (0.0167mol) are slowly added to tetrahydrochysene furan
In muttering, thermotonus 5h is kept, is detected through HPLC, 3,5- dimethylphenylcarbinol conversion ratios are 91.3%, 3,5- dimethyl benzenes
Formaldehyde is selectively 98.2%.Filtrate is concentrated after Filtration of catalyst, and 3,5- dimethyl benzenes are obtained after silica gel column chromatography detaches
Formaldehyde 0.85g, yield：94.5%.1NMR(DMSO-d6):2.31 (s, 6H), 7.38 (d, 2H), 7.60 (m, 1H), 10.8 (s,
1H)。EI-MS m/z:134[M]+。
Embodiment 10
The 3- methylbenzyl alcohols of 0.82g (0.0067mol) and GO-Ti compounds 0.3g are scattered in 10ml tetrahydrofurans
In, 50 DEG C are heated under oil bath, the 30wt% aqueous hydrogen peroxide solutions of 2.66g (0.0234mol) are slowly added in tetrahydrofuran,
Thermotonus 5h is kept, is detected through HPLC, 3- methylbenzyl alcohol conversion ratios are that 88.3%, 3- tolyl aldehydes are selectively
99%.Filtrate is concentrated after Filtration of catalyst, and 3- tolyl aldehyde 0.72g, yield are obtained after silica gel column chromatography detaches：
89.4%.1NMR(DMSO-d6):2.33 (s, 3H), 7.36 (m, 2H), 7.50 (m, 1H), 7.62 (d, 1H), 7.71 (d, 1H),
10.78(s,1H)。EI-MS m/z:120[M]+。
Embodiment 11
The 4- methylbenzyl alcohols of 0.82g (0.0067mol) and GO-Ti compounds 0.3g are scattered in 10ml ethyl alcohol, and
50 DEG C are heated under oil bath, the 30wt% aqueous hydrogen peroxide solutions of 2.66g (0.0234mol) are slowly added in ethyl alcohol.It adds
Thermotonus 5h is kept later, and through HPLC detection 4- methylbenzyl alcohols conversion ratio 89.6%, 4- tolyl aldehydes are selectively
98.6%.Filtrate is concentrated after Filtration of catalyst, and 4- tolyl aldehyde 0.68g, yield are obtained after silica gel column chromatography detaches：
85.2%.1NMR(DMSO-d6):2.29 (s, 3H), 7.41 (m, 2H), 7.75 (m, 2H), 10.71 (s, 1H).EI-MS m/z:
120[M]+。
Embodiment 12
The 2- methylbenzyl alcohols of 0.82g (0.0067mol) and GO-Ti compounds 0.4g are scattered in 10ml tetrahydrofurans
And 60 DEG C are heated under oil bath, the 30wt% aqueous hydrogen peroxide solutions of 2.0g (0.017mol) are slowly added in tetrahydrofuran.
Thermotonus 8h is kept after adding, the conversion ratio that 2- methylbenzyl alcohols are detected through HPLC is 90.2%, 2- tolyl aldehydes
Selectivity be 98.8%.Filtrate is concentrated after Filtration of catalyst, and 2- tolyl aldehydes are obtained after silica gel column chromatography detaches
0.71g, yield 88.1%.1NMR(DMSO-d6):2.45 (s, 3H), 7.23 (d, 1H), 7.47 (m, 1H), 7.62 (m, 1H),
7.75 (d, 1H), 10.92 (s, 1H).EI-MS m/z:120[M]+。
Embodiment 13
The 3,4- dimethylphenylcarbinols of 0.91g (0.0067mol) and GO-Ti compounds 0.35g are scattered in 10ml methanol
In and be heated under oil bath 60 DEG C, the 30wt% aqueous hydrogen peroxide solutions of 2.3g (0.02mol) are slowly added in methanol.It adds
Thermotonus 5h is kept later, and the conversion ratio that 3,4- dimethylphenylcarbinols are detected through HPLC is 90.1%, 3,4- dimethyl benzenes
The selectivity of formaldehyde is 98.5%.Filtrate is concentrated after Filtration of catalyst, and 3,4- diformazans are obtained after silica gel column chromatography detaches
Benzaldehyde 0.79g, yield 87.8%.1NMR(DMSO-d6):2.32 (s, 6H), 7.38 (d, 1H), 7.46 (d, 1H), 7.59
(s, 1H), 10.92 (s, 1H).EI-MS m/z:134[M]+。
Embodiment 14
The 2- naphthalene methanol GO-Ti compounds 0.4g of 1.05g (0.0066mol) is scattered in 10ml tetrahydrofurans and in oil
50 DEG C are heated under bath, the 30wt% aqueous hydrogen peroxide solutions of 1.5g (0.0132mol) are slowly added in tetrahydrofuran.Add it
After keep thermotonus 10h, through HPLC detect 2- naphthalene methanol conversion ratio be 87.6%, 2- naphthaldehydes selectivity be
98.8%.Filtrate is concentrated after Filtration of catalyst, and 2- naphthaldehyde 0.85g, yield are obtained after silica gel column chromatography detaches
82.5%.1NMR(DMSO-d6):7.56 (m, 2H), 7.96 (m, 2H), 8.02 (d, 2H), 8.32 (s, 1H), 10.58 (s, 1H).
EI-MS m/z:156[M]+。
Embodiment 15
By the 1- naphthalenes methanol of 1.05g (0.0066mol) and GO-Ti compounds 0.4g be scattered in 10ml tetrahydrofurans and
70 DEG C are heated under oil bath, the 30wt% aqueous hydrogen peroxide solutions of 1.9g (0.0165mol) are slowly added in tetrahydrofuran.It adds
Thermotonus 10h is kept later, and the conversion ratio that 1- naphthalene methanol is detected through HPLC is that the selectivity of 90.2%, 1- naphthaldehydes is
98.6%.Filtrate is concentrated after Filtration of catalyst, and 1- naphthaldehyde 0.89g, yield are obtained after silica gel column chromatography detaches
86.4%.1NMR(DMSO-d6):7.70 (m, 2H), 7.76 (m, 1H), 8.16 (m, 2H), 8.30 (d, 1H), 9.43 (d, 1H),
10.58(s,1H)。EI-MS m/z:156[M]+。
Embodiment 16
The 4- biphenylmethanols of 1.25g (0.0068mol) and GO-Ti compounds 0.4g are scattered in 10ml tetrahydrofurans simultaneously
70 DEG C are heated under oil bath, the 30wt% aqueous hydrogen peroxide solutions of 2.5 equivalents () are slowly added in tetrahydrofuran.Add it
After keep thermotonus 10h, through HPLC detect 4- biphenylmethanols conversion ratio be 90.6%, 4- biphenylcarboxaldehydes selectivity be
98.2%.Filtrate is concentrated after Filtration of catalyst, and 4- biphenylcarboxaldehyde 1.08g, yield are obtained after silica gel column chromatography detaches
87.4%.1NMR(DMSO-d6):7.43 (m, 1H), 7.56 (m, 4H), 7.86 (d, 2H), 7.96 (d, 2H), 10.58 (s, 1H).
EI-MS m/z:182[M]+。
Claims (10)
1. a kind of with the method that graphene oxide-titanium sulfate nano-complex is catalyst preparation aromatic aldehyde, which is characterized in that will
Reaction raw materials fragrance benzylalcohol is dissolved in organic reagent, homemade graphene oxide-loaded titanium sulfate is added, and be heated to 50-70
DEG C, 10~50% hydrogen peroxide solutions are then added and react 3-12 hours, passes through column chromatography after reaction or vacuum distillation obtains
Product aromatic aldehyde.
2. the method as described in claim 1, which is characterized in that be as follows：
(1) Ti will be contained4+GO-Ti compounds and fragrant benzylalcohol be distributed in organic solvent；
Or directly GO-Ti is distributed in liquid aromatic benzylalcohol reactant；
(2) acquired solution in step (1) is preheating to 30-100 DEG C in temperature constant magnetic stirring oil bath, mixing speed 1000-
2000r/min；
(3) 1~4 times of amount hydrogenperoxide steam generator is directly added into solution described in step (2)；
(4) solution described in step (3) reacts 3~12h, preferably 4~10h at 50-70 DEG C；
(5) Filtration of catalyst, merging filtrate after being washed 2-3 times with organic solvent concentrate, through silica gel column layer after reaction
Analysis separation or vacuum distillation obtain final product aromatic aldehyde.
3. method as claimed in claim 1 or 2, which is characterized in that it is described fragrance benzylalcohol general structure such as (I), (II),
(III) and shown in (IV)；
4. method as claimed in claim 3, which is characterized in that in logical formula (I), (II), (III), (IV), m, n represent substitution
Base number, n=0,1,2,3,4,5；M=0,1,2,3,4.
5. method as claimed in claim 3, which is characterized in that in logical formula (I) (II), (III), (IV), R, R ' be respectively hydrogen,
Halogen, nitro, C1-C5Linear or branched alkyl group.
6. method as claimed in claim 5, which is characterized in that R, R ' are respectively F, Cl, Br, methyl, ethyl or isopropyl.
7. method as claimed in claim 1 or 2, which is characterized in that organic solvent used includes methanol, ethyl alcohol, isopropanol, uncle
Butanol, tetrahydrofuran, acetone, acetonitrile, n,N-Dimethylformamide or Isosorbide-5-Nitrae-dioxane, organic solvent volume used are fragrance
Benzylalcohol quality 5-20 (w/v) times, preferably 10-15 times,；If reaction raw materials and product, which are all liquid, to be had using any
Solvent.
8. method as claimed in claim 1 or 2, which is characterized in that GO-Ti compounds quality used is the 1- of reactant quality
80%, preferably 10-50%.
9. the method as described in right wants 1 or 2, which is characterized in that hydrogen peroxide molal quantity is 2-3 times of reactant in step (3)
Amount, a concentration of the 10~50% of hydrogen peroxide, preferably 30%.
10. method as claimed in claim 1 or 2, which is characterized in that in the graphene oxide-loaded titanium sulfate, titanium sulfate
Quality is the 1-10% of graphene oxide quality.
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Citations (1)
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| CN102177124A (en) * | 2008-10-07 | 2011-09-07 | 宇部兴产株式会社 | Process for producing an aromatic aldehyde compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177124A (en) * | 2008-10-07 | 2011-09-07 | 宇部兴产株式会社 | Process for producing an aromatic aldehyde compound |
Non-Patent Citations (1)
| Title |
|---|
| WENXI MA, QIAOLING TONG, JIAN WANG等: "Synthesis and characterization of titanium(IV)/graphene oxide foam: a sustainable catalyst for the oxidation of benzyl alcohol to benzaldehyde", 《RSC ADVANCES》 * |
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