CN105669484B - A kind of preparation method of amido alkyl naphthols - Google Patents
A kind of preparation method of amido alkyl naphthols Download PDFInfo
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- CN105669484B CN105669484B CN201610134399.1A CN201610134399A CN105669484B CN 105669484 B CN105669484 B CN 105669484B CN 201610134399 A CN201610134399 A CN 201610134399A CN 105669484 B CN105669484 B CN 105669484B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/08—Preparation of carboxylic acid amides from amides by reaction at nitrogen atoms of carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
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Abstract
The present invention relates to a kind of preparation method of amido alkyl naphthols, this method refers to successively add Beta Naphthol 99MIN, aldehyde compound, acid amides and catalyst salicylic acid material in reactor, reacted under 50 ~ 95 DEG C of condition of water bath heating, reactant mixture is obtained after reaction completely；Crude product is obtained after the reactant mixture is scrubbed, the crude product produces pore amide base alkyl naphthol after absolute ethyl alcohol recrystallization separation.The present invention is simple, production cost is low efficiently, and product yield may be up to 92.8%, have preferable prospects for commercial application.
Description
Technical field
The present invention relates to synthetic organic chemical art, more particularly to a kind of preparation method of amido alkyl naphthols.
Background technology
Amido alkyl naphthols, as a kind of important organic synthesis intermediate, because of special bioactivity and pharmacology
Characteristic, there is important use in the synthesis of medicine, agricultural chemicals, asymmetric syntheses and natural products.Particularly by amido alkyl
The derivative for the amido alkyl naphthols that naphthols is transformed has its significant in terms for the treatment of hypertension and angiocardiopathy
Effect.And the part that its derivative is formed also is widely used as catalyst
Patil in 2007 etc. is reported under ultrasonic wave added, and using sulfamic acid as catalyst, betanaphthol, aldehyde and acid amides exist
Reaction obtains corresponding amido alkyl naphthols in dichloromethane or solvent-free medium, although this method yield is high, mild condition,
Reaction time is grown, and most long to need 120min, partial reaction substrate needs addition solvent just to carry out（Sonochemistry
（Ultrasonics Sonochemistry）, 2007, 14, 515–518）.2009, Saidi etc. reported heterogeneous urge
Three component reactions of agent catalysis of phosphotungstic acid aromatic aldehyde, betanaphthol and acid amides, high yield obtain corresponding amido alkyl naphthols.
But need to add etamon chloride in this reaction as co-catalyst, and reaction temperature is higher（100℃）, reaction time length
（80min）（Organic chemistry archives (Archive for Organic Chemistry）2009, vii, 303-310), 303-
310）.Barani in 2015 etc. reports one pot of three component reaction of lactic acid catalysis betanaphthol, aldehyde and acid amides under condition of no solvent,
High yield obtains corresponding product, but this reaction temperature is up to 115 DEG C, and the reaction time is longer, up to 45min（Iran's catalysis journal
（Iranian Journal of Catalysis）, 2015,5,339-343）
Salicylic acid material is usually white crystals, relatively stable in atmosphere at room temperature, is had preferably water-soluble；It is acid
More general organic acid is strong, and post-reaction treatment is simple during as catalyst, is widely used in recent years in organic synthesis.2006,
Khodaei etc. reports p-methyl benzenesulfonic acid and the three of betanaphthol, aldehyde and acid amides is catalyzed in dichloromethane medium or solvent-free medium
Component reaction, high yield obtains corresponding product amide base alkyl naphthol, but this reacts whether solvent-free high temperature（120℃）Reaction
Still reacted at room temperature in dichloromethane, the time is oversize（30~3h）(synthesis bulletin（Synlett）, 2006, 6,
0916-0920 ).And the reaction that current salicylic acid material prepares amido alkyl naphthols for three component one kettle ways yet there are no
Document report.
Although being recorded from document as can be seen that above method reaction condition is gentle, yield is higher, still suffers from many and asks
Topic：(1) need to add co-catalyst；(2) the reaction time is grown；(3) reaction temperature is high；(4) reaction dissolvent, reaction cost height are needed.Therefore
A kind of method of efficient, quick, resource-effective synthesizing amide base alkyl naphthol is developed all the time by the very big pass of people
Note.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of inexpensive, efficient, quick amido alkyl naphthols
Preparation method.
A kind of to solve the above problems, preparation method of amido alkyl naphthols of the present invention, it is characterised in that：Should
Method refers to successively add betanaphthol, aldehyde compound, acid amides and catalyst salicylic acid material in reactor, 50 ~ 95
Reacted under DEG C condition of water bath heating, after reaction completely reactant mixture；Obtain after the reactant mixture is scrubbed and slightly produce
Product, the crude product produce pore amide base alkyl naphthol after absolute ethyl alcohol recrystallization separation；The betanaphthol and salicylic acid
The mol ratio of material is 1：0.02 ~ 0.15, the mol ratio of betanaphthol and aldehyde compound is 1：0.9 ~ 1.3, betanaphthol and acid amides
Mol ratio be 1：0.9~1.2.
The salicylic acid material refers to salicylic acid, 4- cresotinic acids, 4-ASA, 4- chloro-salicylic acids, 5- chlorine
One kind in salicylic acid, acetylsalicylic acid, 5-sulphosalicylic acid.
The structural formula of the aldehyde compound is R1CHO；Wherein R1For aryl or the alkyl containing 2 ~ 7 carbon atoms.
The structural formula of the acid amides is R2CONH2；Wherein R2Alkyl or amino for aryl, containing 2 ~ 4 carbon atoms（NH2）
In one kind.
The reaction temperature is 65 ~ 90 DEG C.
The washing refers to use volume ratio for 1：1 alcohol-water washing.
The present invention has advantages below compared with prior art：
1st, because the present invention uses heating water bath, the category solvent-free cascade reaction method of one pot of three component, therefore so that reaction behaviour
Make step simplification, so as to foreshorten in the reaction time within 15 minutes.
2nd, because the reaction of the present invention is carried out at 50 ~ 95 DEG C, therefore reaction condition is gentle.
3rd, because the present invention is using the good catalyst of activity, catalyst charge once adds all anti-no more than 15%
Material is answered, therefore method is simple, efficient, product yield may be up to 92.8%.
4th, because raw material of the present invention is easy to get, any co-catalyst and solvent are not required to, therefore reduces production cost, have compared with
Good prospects for commercial application.
Embodiment
A kind of preparation method of amido alkyl naphthols of embodiment 1, this method refer to betanaphthol, aldehydes chemical combination successively
Thing, acid amides and catalyst salicylic acid material are added in reactor, are reacted under 50 DEG C of condition of water bath heating, whole reaction
Process is tracked with TLC, i.e., sampled every 1 ~ 2 minute, be respectively dropped into capillary on silica gel plate（Use ethyl acetate
Dissolving）Liquid spotting, material liquid benzaldehyde point sample are reacted, then silica gel plate is put into and filled at two point sample on the same line
Volume ratio（mL/ mL）For 8：In the exhibition bottle of 1 petroleum ether and the mixed liquor of ethyl acetate.After the completion of limp, then silica gel plate put
Observed under uviol lamp or in iodine flask, if the point not flushed in reaction solution with material liquid benzaldehyde, show that reaction is complete,
Now obtain reactant mixture.
Reactant mixture is through volume ratio（mL/ mL）For 1：Crude product is obtained after 1 alcohol-water washing, the crude product is through anhydrous
After ethyl alcohol recrystallization separation, pore amide base alkyl naphthol is produced.
After tested, reaction time 8min, yield 90.3%.
Wherein：Betanaphthol is 1 with salicylic mol ratio：0.05, the mol ratio of betanaphthol and benzaldehyde is 1：1.1, β-
The mol ratio of naphthols and acetamide is 1：1.0.
For a kind of preparation method of amido alkyl naphthols of embodiment 2 with embodiment 1, reaction temperature is 55 DEG C.
After tested, reaction time 10min, yield 83.6%.
Wherein：The mol ratio of betanaphthol and acetylsalicylic acid is 1：0.10, the mol ratio of betanaphthol and 4- tolyl aldehydes
For 1：1.2, the mol ratio of betanaphthol and propionamide is 1：0.9.
For a kind of preparation method of amido alkyl naphthols of embodiment 3 with embodiment 1, reaction temperature is 60 DEG C.
After tested, reaction time 13min, yield 92.8%.
Wherein：The mol ratio of betanaphthol and 5- chloro-salicylic acids are 1：0.08, the mol ratio of betanaphthol and 4- chlorobenzaldehydes is
1：1.3, the mol ratio of betanaphthol and benzamide is 1：1.0.
For a kind of preparation method of amido alkyl naphthols of embodiment 4 with embodiment 1, reaction temperature is 65 DEG C.
After tested, reaction time 10min, yield 60.3%.
Wherein：The mol ratio of betanaphthol and 5-sulphosalicylic acid is 1：0.10, the mol ratio of betanaphthol and 4- chlorobenzaldehydes
For 1：1.2, the mol ratio of betanaphthol and benzamide is 1：1.1.
For a kind of preparation method of amido alkyl naphthols of embodiment 5 with embodiment 1, reaction temperature is 70 DEG C.
After tested, reaction time 7min, yield 67.8%.
Wherein：The mol ratio of betanaphthol and 5-sulphosalicylic acid is 1：0.15, the mol ratio of betanaphthol and n-Heptaldehyde is 1：
1.3, the mol ratio of betanaphthol and benzamide is 1：1.0.
For a kind of preparation method of amido alkyl naphthols of embodiment 6 with embodiment 1, reaction temperature is 75 DEG C.
After tested, reaction time 15min, yield 90.7%.
Wherein：Betanaphthol is 1 with salicylic mol ratio：0.05, the mol ratio of betanaphthol and 2,4- dichlorobenzaldehyde is
1：1.2, the mol ratio of betanaphthol and urea is 1：1.1.
For a kind of preparation method of amido alkyl naphthols of embodiment 7 with embodiment 1, reaction temperature is 80 DEG C.
After tested, reaction time 6min, yield 92.1%.
Wherein：The mol ratio of betanaphthol and 4- chloro-salicylic acids are 1：0.02, the mol ratio of betanaphthol and 4- cyanobenzaldehydes
For 1：1.0, the mol ratio of betanaphthol and acetamide is 1：1.2.
For a kind of preparation method of amido alkyl naphthols of embodiment 8 with embodiment 1, reaction temperature is 85 DEG C.
After tested, reaction time 10min, yield 87.3%.
Wherein：The mol ratio of betanaphthol and 4- cresotinic acids is 1：0.10, the mol ratio of betanaphthol and 4- bromobenzaldehydes
For 1：1.2, the mol ratio of betanaphthol and propionamide is 1：1.0.
For a kind of preparation method of amido alkyl naphthols of embodiment 9 with embodiment 1, reaction temperature is 90 DEG C.
After tested, reaction time 12min, yield 70.2%.
Wherein：The mol ratio of betanaphthol and 4-ASA is 1：0.05, the mol ratio of betanaphthol and 4- benzonitrile formaldehyde
For 1：1.0, the mol ratio of betanaphthol and butyramide is 1：1.2.
For a kind of preparation method of amido alkyl naphthols of embodiment 10 with embodiment 1, reaction temperature is 95 DEG C.
After tested, reaction time 10min, yield 84.6%.
Wherein：The mol ratio of betanaphthol and 5-sulphosalicylic acid is 1：0.02, mole of betanaphthol and 4- nitrobenzaldehydes
Than for 1：0.9, the mol ratio of betanaphthol and acetamide is 1：1.1.
For a kind of preparation method of amido alkyl naphthols of embodiment 11 with embodiment 1, reaction temperature is 50 DEG C.
After tested, reaction time 15min, yield 64.3%.
Wherein：Betanaphthol and salicylic acid and mol ratio be 1：0.15, the mol ratio of betanaphthol and n-butanal is 1：1.3
The mol ratio of betanaphthol and benzamide is 1：1.2.
For a kind of preparation method of amido alkyl naphthols of embodiment 12 with embodiment 1, reaction temperature is 55 DEG C.
After tested, reaction time 9min, yield 90.1%.
Wherein：The mol ratio of betanaphthol and 5-sulphosalicylic acid is 1：0.05, the mol ratio of betanaphthol and 2- bromobenzaldehydes
For 1：1.2, the mol ratio of betanaphthol and propionamide is 1：1.1.
For a kind of preparation method of amido alkyl naphthols of embodiment 13 with embodiment 1, reaction temperature is 60 DEG C.
After tested, reaction time 15min, yield 70.1%.
Wherein：The mol ratio of betanaphthol and 4-ASA is 1：0.10, betanaphthol and 4-methoxybenzaldehyde rub
You are than being 1：0.9, the mol ratio of betanaphthol and urea is 1：1.1.
Claims (2)
- A kind of 1. preparation method of amido alkyl naphthols, it is characterised in that：This method refers to betanaphthol, aldehydes chemical combination successively Thing, acid amides and catalyst salicylic acid material are added in reactor, are reacted under 50 ~ 95 DEG C of condition of water bath heating, are reacted Reactant mixture is obtained after completely；Crude product is obtained after the reactant mixture is scrubbed, the crude product is through absolute ethyl alcohol recrystallization point From rear, pore amide base alkyl naphthol is produced；The mol ratio of the betanaphthol and salicylic acid material is 1：0.02 ~ 0.15, β- The mol ratio of naphthols and aldehyde compound is 1：0.9 ~ 1.3, the mol ratio of betanaphthol and acid amides is 1：0.9~1.2；The bigcatkin willow Acid refers to salicylic acid, 4- cresotinic acids, 4-ASA, 4- chloro-salicylic acids, 5- chloro-salicylic acids, acetyl salicylic One kind in acid, 5-sulphosalicylic acid；The structural formula of the aldehyde compound is R1CHO；Wherein R1For aryl or containing 2 ~ 7 carbon The alkyl of atom；The structural formula of the acid amides is R2CONH2；Wherein R2Alkyl or amino for aryl, containing 2 ~ 4 carbon atoms （NH2）In one kind.
- A kind of 2. preparation method of amido alkyl naphthols as claimed in claim 1, it is characterised in that：The washing refers to adopt It is 1 with volume ratio：1 alcohol-water washing.
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