CN104311376A - New method for directly preparing aryl aldehyde from aryl nitrile - Google Patents
New method for directly preparing aryl aldehyde from aryl nitrile Download PDFInfo
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- CN104311376A CN104311376A CN201410478142.9A CN201410478142A CN104311376A CN 104311376 A CN104311376 A CN 104311376A CN 201410478142 A CN201410478142 A CN 201410478142A CN 104311376 A CN104311376 A CN 104311376A
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- acetic acid
- aryl
- nitrile
- fragrant nitrile
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Abstract
The invention provides a method for directly preparing aryl aldehyde from aryl nitrile. The method is characterized in that the aryl nitrile is further reduced by pyridine and sodium hypophosphite in an acetic acid-water solution in nitrogen atmosphere under the catalysis of Rainie nickel in order to form aryl aldehyde. The acetic acid-water solution is used as a reaction solvent, hypophosphorous acid generated through a reaction of sodium hypophosphite and acetic acid reacts with pyridine to form a salt, and the aryl nitrile is directly reduced by in situ hydrogen released by the salt under the catalysis of the Rainie nickel to form the aryl aldehyde. The method has the advantages of fast reaction, easy operation, easily available raw materials, mild conditions, high yield, and suitableness for industrial preparation.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly a kind of novel method directly being prepared aromatic aldehyde by fragrant nitrile.
Background technology
Virtue nitrile is as a kind of common synthetic intermediate be easy to get, and its preparation method is a lot, as being obtained by reacting fragrant nitrile by halogenated aryl hydrocarbon and cuprous cyanide, also obtains fragrant nitrile by aromatic primary amine through Sandmeyer diazotization reaction.
Aromatic aldehyde is a kind of important chemical intermediate, and its chemically reactive is comparatively strong, and number of chemical reaction can occur, and its aldehyde functions is quite important in organic synthesis.
The method directly being prepared aromatic aldehyde by fragrant nitrile has larger using value.The technological method at present preparing aromatic aldehyde by fragrant nitrile mainly contains following several:
1) people such as Fred Xi, Fred Kamal uses platinum oxide to make catalyzer in " A novel and convenient transformation of nitriles to aldehydes ", and formic acid is that fragrant nitrile is reduced to aromatic aldehyde by reductive agent;
2) people such as A.Chatterjee, R.A.Shaikh report ruthenium/zeolite, platinum/zeolites as catalysts in " Direct reductive hydrolysis ofnitriles to aldehydesover Ru-and Pt-loaded zeolites " passes into hydrogen by fragrant nitrile and is reduced to aromatic aldehyde;
3) people such as Bui The Khai, Antonio Arcelli is at " A New Hydrogen Source.3.Chemoselective Reduction with Et
3nH
+h
2pO
2 - *nH
20/Raney Nickel and RuCl
2(PPh
3)
3" mention in a literary composition add Et in the reaction system of THF and ethanol as solvent
3nH
+h
2pO
2 -* 1.5H
2the fragrant nitrile that reduces in O/Raney Ni is aromatic aldehyde;
4) Kei Goto, Junji Kobayashi etc. are at " Synthesis, Structure, and Reducing Ability of a Stable Organotrihydroaluminate Bearing a Novel Bowl-Type Substituent " middle synthetic catalyst BmtAlH
3li (DME)
2, reduce fragrant nitrile with it;
5) A.ff.Finhoi.TE etc. use tetrahydrochysene aluminium sodium in " Organic Reductions by Sodium Aluminum Hydride ", Alfrede E.G. etc. use dialkyl group aluminum hydride in " Reductions with Dialkylaluminum Hydrides ", and fragrant nitrile is reduced to aromatic aldehyde.
Make a general survey of these are prepared aromatic aldehyde technological method by fragrant nitrile, usual step is complicated, and reaction conditions is harsh, processing safety is low, reaction reagent is rare, and have that productive rate is low, by product is many (as aldehyde is become alcohol by over reduction), the defects such as reactive chemistry selectivity is low.
Summary of the invention
Goal of the invention: the object of the invention is to provide a kind of method directly being prepared aromatic aldehyde by fragrant nitrile that technique is simple, mild condition, productive rate are high.
Technical scheme: the present invention is to provide a kind of method directly being prepared aromatic aldehyde by fragrant nitrile: in aqueous acetic acid, fragrant nitrile one step is reduced to aromatic aldehyde by pyridine and inferior sodium phosphate in nitrogen atmosphere, under raney ni catalysis;
Its reaction formula is as follows:
As preferably, the reaction times is 7h, and temperature of reaction is 100 DEG C.
Preferred as another kind, the aryl in described fragrant nitrile is aromatic ring, condensed ring or heterocycle wait substituting group, preferably phenyl, pyridyl, furyl, pyrryl, naphthyl, indyl, benzofuryl.
Preferred as another kind, the mass percentage of described glacial acetic acid aqueous solution is 55%.
Preferred as another kind, the mol ratio of described pyridine, inferior sodium phosphate and fragrant nitrile is 1.5:2:1.
Beneficial effect: method provided by the invention take aqueous acetic acid as reaction solvent, acetic acid and inferior sodium phosphate react the ortho phosphorous acid that generates and pyridine reacts salify.This pyridinium salt discharges in-situ hydrogen and directly fragrant nitrile one step is reduced to aromatic aldehyde under raney ni catalysis, simple and efficient to handle, and raw material is common to be easy to get, and reactions steps is few, mild condition, and productive rate is high, and reaction is almost quantitative reaction.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
The preparation of Raney's nickel: according to common synthetic method, the W type Raney's nickel catalyst that alumino nickel is prepared in alkali lye is all applicable to the reaction directly being prepared aromatic aldehyde by fragrant nitrile of the present invention.
Implement logical method:
Difference unit temp meter and agitator on 250ml there-necked flask; pass into nitrogen protection; add pyridine, Glacial acetic acid, inferior sodium phosphate, water, fragrant nitrile, Raney's nickel catalyst; agitation condition next stage temperature reaction H hour (TLC monitors reaction process); heating is stopped, cooling after reacting completely.Separating-purifying is carried out to product.
Specific embodiment the results are shown in Table 1, and Characterization of The Products data are in table 2.
Embodiment 1
The method of phenyl aldehyde is prepared by cyanobenzene.
On 250ml there-necked flask, difference unit temp meter and agitator, pass into nitrogen protection system, add 28.6ml Glacial acetic acid (0.5mol; 30.0g), 30ml water, forms 50% aqueous acetic acid; add 12.1ml pyridine (0.15mol, 11.9g) again, 17.6g inferior sodium phosphate (0.2mol); cyanobenzene 10.2ml (0.1mol, 10.3g), W3 type Raney's nickel catalyst 1g; stir, be warming up to 80 DEG C, react after 5 hours; stop heating, cooling.With dichloromethane extraction (50ml × 3), merge organic phase, anhydrous sodium sulfate drying after three washings, Filtration of catalyst powder and siccative, after filtrate steaming removal solvent, underpressure distillation, collects 56-58 DEG C/10mmHg cut, obtain colourless liquid phenyl aldehyde 8.3g (productive rate 78%), Characterization of The Products data are in table 2.
Embodiment 2
The method of Benzaldehyde,2-methoxy is prepared by 2-methoxy benzonitrile.
Difference unit temp meter and agitator on 250ml there-necked flask; pass into nitrogen protection system; add 31.5ml Glacial acetic acid (0.55mol; 33.0g); 27ml water; form 55% aqueous acetic acid; add 12.1ml pyridine (0.15mol, 11.9g) again, 17.6g inferior sodium phosphate (0.2mol); 2-methoxy benzonitrile 12.2ml (0.1mol; 13.3g), W2 type Raney's nickel catalyst 1g, stirs; be heated to 80 DEG C of reactions after 5 hours, continue to be heated to 100 DEG C of reactions 2 hours.Stopped reaction, cooling.After filtration catalizer powder, decompression steams low boil-off dose, and obtained aqueous solution is extracted with ethyl acetate.Merge organic layer, removed under reduced pressure major part solvent after dry, freezing and crystallizing, obtain product as light yellow solid Benzaldehyde,2-methoxy 12.4g (productive rate 91%), Characterization of The Products data are in table 2.
Embodiment 3
The method of terephthalaldehydic acid methyl esters is prepared by paracyanobenzoic acid methyl esters.
Difference unit temp meter and agitator on 250ml there-necked flask; pass into nitrogen protection system; add 31.5ml Glacial acetic acid (0.55mol; 33.0g), 27ml water, forms 55% aqueous acetic acid; add 12.1ml pyridine (0.15mol again; 11.9g), 13.2g inferior sodium phosphate (0.15mol), paracyanobenzoic acid methyl esters 16.1g (0.1mol); W1 type Raney's nickel catalyst 1g; stir, and system temperature is risen to 60 DEG C, react after 6 hours; system temperature is risen to 90 DEG C; after reacting 4 hours again, stop heating, cooling.With dichloromethane extraction (50ml × 3), merge organic phase, use a small amount of water washing three times again, after anhydrous sodium sulfate drying, Distillation recovery partial solvent, crystallisation by cooling obtains white powdery solids terephthalaldehydic acid methyl esters 14.6g (productive rate 89%), and Characterization of The Products data are in table 2.
Embodiment 4
The method of 1-naphthaldehyde is prepared by 1-naphthyl cyanide.
Difference unit temp meter and agitator on 250ml there-necked flask, pass into nitrogen protection system, add 37.2ml Glacial acetic acid (0.65mol, 39.0g), 27ml water, form 60% aqueous acetic acid, add 16.1ml pyridine (0.2mol again, 15.82g), 17.6g inferior sodium phosphate (0.2mol), 1-naphthyl cyanide 15.3g (0.1mol), W4 type Raney's nickel catalyst 1g, stir, and system temperature is risen to 110 DEG C, react after 5 hours, stop heating, cooling, with dichloromethane extraction (50ml × 3), merge organic phase, a small amount of washing, with anhydrous sodium sulfate drying, filter, after filtrate steaming removal solvent, underpressure distillation, collect 160-165 DEG C/20mmHg cut, obtain weak yellow liquid 1-naphthaldehyde 12.9g (productive rate 83%), Characterization of The Products data are in table 2.
Embodiment 5
The method of 2,6-dialdehyde-based naphthalene is prepared by 2,6-dicyano naphthalene.
Difference unit temp meter and agitator on 250ml there-necked flask; pass into nitrogen protection system; add 45.8ml Glacial acetic acid (0.8mol, 48.0g), 26ml water; form 65% aqueous acetic acid; add 20.1ml pyridine (0.25mol, 19.8g) again, 22.0g inferior sodium phosphate (0.25mol); 2; 6-dicyano naphthalene 17.8g (0.1mol), W2 type Raney's nickel catalyst 1g, stir; and system temperature is risen to 120 DEG C; react after 4 hours, system temperature is risen to 150 DEG C, then after reacting 3 hours; stop heating, cooling.With dichloromethane extraction (50ml × 3), merge organic phase, use a small amount of water washing three times again, with anhydrous sodium sulfate drying, filter, air distillation recovery part solvent, recrystallization obtains white powder product 2,6-dialdehyde-based naphthalene 16.6g (productive rate 90%), Characterization of The Products data are in table 2.
Embodiment 6
4 are prepared, 4 '-diphenyl-dimethanal by 4,4 '-biphenyl dimethoxy nitrile.
Difference unit temp meter and agitator on 250ml there-necked flask, pass into nitrogen protection system, add 45.8ml Glacial acetic acid (0.8mol, 48.0g), 26ml water, form 65% aqueous acetic acid, add 20.1ml pyridine (0.25mol again, 19.8 gram), 22.0g inferior sodium phosphate (0.25mol), 4, 4 '-biphenyl dimethoxy nitrile 20.4g (0.1mol), W5 type Raney's nickel catalyst 1g, stir, and system temperature is risen to 100 DEG C, react after 3 hours, system temperature is risen to 130 DEG C, after reacting 3 hours again, stop heating, cooling, with dichloromethane extraction (50ml × 3), merge organic phase, use a small amount of water washing three times again, after anhydrous sodium sulfate drying, steam the most of solvent of removing, crystallisation by cooling, obtain white crystal 4, 4 '-diphenyl-dimethanal 17.0g (productive rate 81%), Characterization of The Products data are in table 2.
Embodiment 7
The method of 3-aldehyde radical pyridine is prepared by nicotinonitrile.
Difference unit temp meter and agitator on 250ml there-necked flask, pass into nitrogen protection system, add 28.6ml Glacial acetic acid (0.5mol, 30.0g), 30ml water, form 50% aqueous acetic acid, add 24.2ml pyridine (0.3mol again, 23.7g), 26.4g inferior sodium phosphate (0.3mol), nicotinonitrile 10.4g (0.1mol), W2 type Raney's nickel catalyst 1g, stir, and system temperature is risen to 110 DEG C, react after 4 hours, stop heating, cooling, with dichloromethane extraction (50ml × 3), merge organic phase, use a small amount of water washing three times again, after organic phase drying, steaming desolventizes, underpressure distillation, collect 94-97 DEG C/15mmHg cut, obtain light yellow liquid 3-aldehyde radical pyridine 7.8g (productive rate 73%), Characterization of The Products data are in table 2.
Embodiment 8
The method of 2 furan carboxyaldehyde is prepared by 2-furans formonitrile HCN.
Difference unit temp meter and agitator on 250ml there-necked flask, pass into nitrogen protection system, add 31.5ml Glacial acetic acid (0.55mol, 33.0g), 27ml water, form 55% aqueous acetic acid, add 12.1ml pyridine (0.15mol again, 11.9g), 17.6g inferior sodium phosphate (0.2mol), 2-furans formonitrile HCN 8.8ml (0.1mol, 9.3g), W3 type Raney's nickel catalyst 1g, stir, and system temperature is risen to 100 DEG C, react after 7 hours, stop heating, cooling, with dichloromethane extraction (50ml × 3), merge organic phase, washing once, steam distillation distills, separatory obtains yellow liquid 2 furan carboxyaldehyde 8.4g (productive rate 87%), Characterization of The Products data are in table 2.
Embodiment 9
The method of 2-pyrrole aldehyde is prepared by 2-pyrrolecarbonitrile.
Difference unit temp meter and agitator on 250ml there-necked flask; pass into nitrogen protection system; add 37.2ml Glacial acetic acid (0.65mol; 39.0g), 27ml water, forms 60% aqueous acetic acid; add 12.1ml pyridine (0.15mol again; 11.9g), 13.2g inferior sodium phosphate (0.15mol), 2-pyrrolecarbonitrile 9.2g (0.1mol); W1 type Raney's nickel catalyst 1g; stir, and system temperature is risen to 100 DEG C, react after 7 hours; system temperature is risen to 120 DEG C; after reacting 2 hours again, stop heating, cooling.With dichloromethane extraction (50ml × 3), merge organic phase, once, precipitation after dry, crystallisation by cooling, obtain White crystalline product 2-pyrrole aldehyde 8.4g (productive rate 77%), Characterization of The Products data are in table 2 in washing.
Embodiment 10
The method of 3-indolecarboxaldehyde is prepared by 3-indoles formonitrile HCN.
Difference unit temp meter and agitator on 250ml there-necked flask, pass into nitrogen protection system, add 31.5ml Glacial acetic acid (0.55mol, 33.0g), 27ml water, form 55% aqueous acetic acid, add 12.1ml pyridine (0.15mol again, 11.9g), 17.6g inferior sodium phosphate (0.2mol), 3-indoles formonitrile HCN 14.2g (0.1mol), W2 type Raney's nickel catalyst 1g, stir, and system temperature is risen to 95 DEG C, react after 3 hours, system temperature is risen to 110 DEG C, after reacting 3 hours again, stop heating, cooling, with chloroform extraction (50ml × 3), merge organic phase, washing, steam after dry and desolventize, recrystallization obtains pale yellow crystals product 3-indolecarboxaldehyde 12.2g (productive rate 84%), Characterization of The Products data are in table 2.Embodiment 11
The method of 4-indolecarboxaldehyde is prepared by 4-indoles formonitrile HCN.
Difference unit temp meter and agitator on 250ml there-necked flask, pass into nitrogen protection system, add 31.5ml Glacial acetic acid (0.55mol, 33.0g), 27ml water, form 55% aqueous acetic acid, add 12.1ml pyridine (0.15mol again, 11.9g), 13.2g inferior sodium phosphate (0.15mol), 4-indoles formonitrile HCN 14.2g (0.1mol), W2 type Raney's nickel catalyst 1g, stir, and system temperature is risen to 110 DEG C, react after 4 hours, system temperature is risen to 130 DEG C, after reacting 2 hours again, stop heating, cooling, with dichloromethane extraction (50ml × 3), merge organic phase, washing, steam after dry and desolventize, recrystallization obtains off-white color crystalline powder 4-indolecarboxaldehyde 12.3g (productive rate 85%), Characterization of The Products data are in table 2.
Embodiment 12
The method of 3-aldehyde radical cumarone is prepared by 3-cyano group cumarone.
Difference unit temp meter and agitator on 250ml there-necked flask, pass into nitrogen protection system, add 28.6ml Glacial acetic acid (0.5mol, 30.0g), 30ml water, form 50% aqueous acetic acid, add 8.1ml pyridine (0.1mol again, 7.9g), 8.8g inferior sodium phosphate (0.1mol), 3-cyano group cumarone 14.3g (0.1mol), W3 type Raney's nickel catalyst 1g, stir, and system temperature is risen to 95 DEG C, react after 6 hours, stop heating, cooling, with toluene extraction (50ml × 3), merge organic phase, washing, steam after dry and desolventize, crystallisation by cooling obtains off-white color solid 3-aldehyde radical cumarone 10.8g (productive rate 74%), Characterization of The Products data are in table 2.
Embodiment 13
The method of 3-indolecarboxaldehyde is prepared by 3-indoles formonitrile HCN.
In 500L reactor, pass into nitrogen protection system, add 66kg Glacial acetic acid, 54L water, form 55% aqueous acetic acid, add 24kg pyridine again, 35kg inferior sodium phosphate, 3-indoles formonitrile HCN 28.5kg, W2 type Raney's nickel catalyst 2kg, stir, and system temperature is risen to 100 DEG C, react after 3 hours, system temperature is risen to 110 DEG C, after reacting 3 hours again, stop heating, cooling, with toluene extraction (250L × 3), merge organic phase, washing, steam after dry and desolventize, after activated carbon decolorizing, crystallisation by cooling obtains pale yellow crystals product 3-indolecarboxaldehyde 24.0kg (productive rate 82%).
Table 1 specific embodiment result
Note: a: react and complete through a stage.
B: react and complete through two stages.
C: productive rate is recorded by gas-chromatography.
D: be liquid under portion of product room temperature (25 DEG C), therefore provide the theoretical boiling point under its 20mmHg pressure.
Table 2 product IR characterization data (cm
-1)
* number be mass-spectrometric data.
Claims (5)
1. directly prepared a method for aromatic aldehyde by fragrant nitrile, it is characterized in that: in aqueous acetic acid, fragrant nitrile one step is reduced to aromatic aldehyde by pyridine and inferior sodium phosphate in nitrogen atmosphere, under raney ni catalysis;
Its reaction formula is as follows:
。
2. a kind of method directly being prepared aromatic aldehyde by fragrant nitrile according to claim 1, it is characterized in that: the reaction times is 4-10h, temperature of reaction is 60-150 DEG C.
3. a kind of method by the direct aromatic aldehyde of fragrant nitrile according to claim 1, it is characterized in that: the aryl in described fragrant nitrile be aromatic ring, condensed ring or heterocycle etc. substituting group, be preferably phenyl, pyridyl, furyl, pyrryl, naphthyl, indyl, benzofuryl.
4. a kind of method directly being prepared aromatic aldehyde by fragrant nitrile according to claim 1, is characterized in that: the mass percentage of described glacial acetic acid aqueous solution is 50%-65%.
5. a kind of method directly being prepared aromatic aldehyde by fragrant nitrile according to claim 1, is characterized in that: the mol ratio of described pyridine, inferior sodium phosphate and fragrant nitrile is (1-3): (1-3): 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106397149A (en) * | 2016-08-26 | 2017-02-15 | 大连奇凯医药科技有限公司 | Preparation method of pentafluorobenzaldehyde |
| CN106946677A (en) * | 2017-04-20 | 2017-07-14 | 深圳市华星光电技术有限公司 | Fused ring compound and its application, electroluminescent device and preparation method thereof |
| CN108503621A (en) * | 2017-12-25 | 2018-09-07 | 上海中拓医药科技有限公司 | A kind of preparation method of Vonoprazan fumarate |
| CN113248355A (en) * | 2021-07-07 | 2021-08-13 | 山东国邦药业有限公司 | Preparation method of p-chlorobenzaldehyde |
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| CN1483712A (en) * | 2002-08-14 | 2004-03-24 | Catalytic reduction method of benzonitrile to benzoaldehyde |
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| CN1483712A (en) * | 2002-08-14 | 2004-03-24 | Catalytic reduction method of benzonitrile to benzoaldehyde |
Non-Patent Citations (2)
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| MAKOTO SHIMIZU ET AL.,: "Efficient Pyrrole Synthesis Using Double Nucleophilic Addition to α, β-Unsaturated Imines with Plural Nucleophiles", 《ORG. LETT.》, vol. 8, no. 16, 8 July 2006 (2006-07-08) * |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397149A (en) * | 2016-08-26 | 2017-02-15 | 大连奇凯医药科技有限公司 | Preparation method of pentafluorobenzaldehyde |
| CN106397149B (en) * | 2016-08-26 | 2019-05-21 | 大连奇凯医药科技有限公司 | The preparation method of pentafluorobenzaldehyde |
| CN106946677A (en) * | 2017-04-20 | 2017-07-14 | 深圳市华星光电技术有限公司 | Fused ring compound and its application, electroluminescent device and preparation method thereof |
| CN106946677B (en) * | 2017-04-20 | 2019-07-12 | 深圳市华星光电半导体显示技术有限公司 | Fused ring compound and its application, electroluminescent device and preparation method thereof |
| US10424738B2 (en) | 2017-04-20 | 2019-09-24 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd | Condensed-cyclic compound, electroluminescent device and method for manufacturing thereof |
| CN108503621A (en) * | 2017-12-25 | 2018-09-07 | 上海中拓医药科技有限公司 | A kind of preparation method of Vonoprazan fumarate |
| CN108503621B (en) * | 2017-12-25 | 2021-09-14 | 上海中拓医药科技有限公司 | Preparation method of vonoprazan fumarate |
| CN113248355A (en) * | 2021-07-07 | 2021-08-13 | 山东国邦药业有限公司 | Preparation method of p-chlorobenzaldehyde |
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Application publication date: 20150128 |