CN105367436B - A kind of preparation method of N, N- mesitylenic acid ester type compound - Google Patents
A kind of preparation method of N, N- mesitylenic acid ester type compound Download PDFInfo
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Abstract
The present invention relates to a kind of N, the preparation method of N mesitylenic acid ester type compounds, more particularly to N, N dimethylanilines, double (trichloromethyl) carbonic esters and alcohol prepare N for raw material, the preparation method of N mesitylenic acid esters, this method raw material is cheap and easy to get, high income, and intermediate, which is not required to purification, does not need to change solvent, to be a kind of cheap, environmentally friendly, easy to operate, suitable industrialized preparation method with successive reaction.And N, N dimethyl benzoyl chlorides important chemical industry and medicine intermediate can also be prepared using this method.
Description
Technical field
The present invention relates to a kind of N, the preparation method of N- mesitylenic acid ester type compounds, and in particular to N, N- diformazans
Base aniline, double (trichloromethyl) carbonic esters and alcohol prepare N, the preparation method of N- mesitylenic acid esters, this method original for raw material
Expect cheap and easy to get, high income, intermediate, which is not required to purification, does not need to change solvent, to be a kind of cheap, environmental protection, easy with successive reaction
Operation, suitable industrialized preparation method.And N, the important change of N- dimethyl benzoyl chlorides can also be prepared using this method
Work and medicine intermediate.
Background technology
Dimethylaminobenzoic acid ester type compound is a kind of organic matter for having extensive use, is common organic base, phase turn
Shifting catalyst, amine promoter, fungicide, preservative, sun-screening agent, fine-chemical intermediate, medicine intermediate etc..To diformazan ammonia
Yl benzoic acid ester type compound is a kind of efficient amine promoter, same to free radical（II）Type photoinitiator is used together, extensive
Be used for paper, timber, the varnish paint system of metal and frosting, ink, adhesive etc. carry out ultraviolet light curing；
Can be also used for single or various of monomer ultraviolet radiation polymerisation, but also be good sensitizer, often with other light
Initiator is used in combination, such as：Thioxanthones, acetophenones light trigger, can promote photoinitiation and effectively eliminate
The interference effect that oxygen polymerize photoinitiator.This series compound has had a large amount in variety at present, such as：P-(dimethylamino)-benzoic acid second
Ester（EBD）, isooctyl p-dimethylaminobenzoate（EHA, trade name 507）, isoamyl p-dimethylaminobenzoate（DMBI）、
P-(dimethylamino)-benzoic acid methyl esters, p-(dimethylamino)-benzoic acid propyl ester, p-(dimethylamino)-benzoic acid N-butyl etc., 2- dimethylaminos
Ethyl benzoate.
P-(dimethylamino)-benzoic acid ester series compound is a kind of good UVB areas ultra-violet absorber, is also used as
Excellent uvioresistant additive, is widely used in water-fast sun care preparations, and wherein EHA is classified as first by U.S. FDA and analogizes
Recommend the sun-screening agent used.Meanwhile p-(dimethylamino)-benzoic acid ester series compound can also be used as preservative, to diformazan ammonia
Yl benzoic acid methyl esters, p-(dimethylamino)-benzoic acid propyl ester, p-(dimethylamino)-benzoic acid N-butyl and its solution all there is anti-corrosion to make
With.
Existing p-(dimethylamino)-benzoic acid ester series compound preparation method has three kinds：
1）, p-(dimethylamino)-benzoic acid be directly esterified, generally make catalyst with acid（ Bioorganicand
Medicinal Chemistry, 18（22）：7836-7841；2010）Esterification is carried out with correspondent alcohol；
2）, P aminobenzoates carry out N-methyl, the reagent to methylate is usually dimethyl suflfate（Journal of
The Chemical Society, Chemical Communications, 17：1202-1203,1985）, formaldehyde cyano group boron hydrogen
Change sodium（Journalof the American Chemical Society, 120（2）：5193-5202,1998）, iodomethane
（Journal of Organic Chemistry, 75（5）：1378-1385,2010）；
3）, using paradime thylaminobenzaldehyde as raw material, in catalyst silver oxide or silver nitrate（Huaihai Institute of Technology journal（From
Right science version）, 14（2）：53-55,2005）Under the action of be oxidized to p-(dimethylamino)-benzoic acid, be then esterified under acid catalysis.
Or four（Triphenylphosphine）Under palladium and benzyl bromine co-catalysis（Tetrahedron Letters, 52（41）：5319-5322,
2011）Or 1,2- dimethyl indazole -3- formates（Organic Letters, 9（18）：3515-3518,2007）Catalysis it is lower with
P-(dimethylamino)-benzoic acid ester is made in correspondent alcohol reaction.
Method 1）There are the problem of be esterification yield it is low, cause production cost higher, but also produce substantial amounts of acid
Waste water, environment are unfriendly；Method 2）The shortcomings that to be that N-methyl is difficult complete, dimethyl suflfate toxicity is larger, and waste water is more, iodine first
Alkane, sodium cyanoborohydride toxicity are of high cost greatly；Method 3）Avoid, using the larger reagent of toxicity, spent acidic will not being produced
Water, but used the high precious metal chemical complex of price, four（Triphenylphosphine）Palladium and benzyl bromine catalyst or indazole salt catalyst, are urged
Agent is of high cost and dosage is big, therefore causes whole cost very high, is not suitable for industrialized production.
2- dimethyl ethyl aminobenzoates are not only used in photocuring system, while still important chemical intermediate
And medicine intermediate, its preparation method are reported less at present.Dimethylamino chlorobenzoyl chloride is also very important fine chemistry industry
Intermediate and medicine intermediate.The preparation method of dimethylamino chlorobenzoyl chloride is usually raw material by dimethylaminobenzoic acid, is led to
To cross and be prepared with the oxalyl chloride of highly acid, thionyl chloride, phosgene, phosphorus pentachloride back flow reaction, such method cost of material is high,
Height is required to reaction kettle, and has acid gas generation, it is unfavorable to environment.
The content of the invention
The shortcomings that the purpose of the present invention is overcoming present in existing preparation method, there is provided a kind of raw material is cheap and easy to get, uses
Safety, reaction condition it is gentle easy to operate and also reach high-purity, in high yield, the dimethylaminobenzoic acid that the three wastes are few, environmental-friendly
The preparation method of ester type compound.This method is using n,N-Dimethylaniline, double (trichloromethyl) carbonic esters and alcohol as raw material, N, N-
After dimethylaniline and double (trichloromethyl) carbonate reactions, obtained intermediate carries out alcoholysis；Or dimethylamino-aniline and
Dimethylamino chlorobenzoyl chloride intermediate is obtained through processing later after double (trichloromethyl) carbonate reactions, alcohol is then carried out again and solves
To dimethylaminobenzoic acid ester type compound.Technique provided by the invention is simple, and operation is easy, and cost is low, high income, and product is pure
Degree is high, no matter solid product or product liquid, appearance is preferable, environmentally friendly, meets environmentally protective requirement, has notable
Social benefit and economic benefit, be adapted to industrialized production.
In order to achieve the above object, the preparation method of dimethylaminobenzoic acid ester type compound provided by the invention, with N,
Accelerine is raw material.Dimethylaminobenzoic acid ester type compound and as follows with N, the structural formula of accelerine：
Wherein, R represents the alkyl of 1-8 carbon atom.
Its synthesis step is：
Wherein, R represents the alkyl of 1-8 carbon atom.
One kind provided by the invention prepares dimethylamino chlorobenzoyl chloride（Formula III）：
Pass through N, accelerine（Formula II）, in the case where being present with or without solvent, with double (trichloromethyl) carbonic acid
It is prepared by ester reaction.
One kind provided by the invention prepares dimethylaminobenzoic acid ester type compound（Formulas I）：
Wherein, R represents the alkyl of 1-8 carbon atom.
1）Pass through N, accelerine（Formula II）, in the case where being present with or without solvent, with double (trichloromethyl) carbon
Acid esters reacts；With
2）Then reacted with alcohol；
This method need not separate intermediate product dimethylamino chlorobenzoyl chloride.
One kind provided by the invention prepares dimethylamino chlorobenzoyl chloride（Formula III）Specific steps：
1）, n,N-Dimethylaniline is dissolved in solvent, double (trichloromethyl) carbonic esters are slowly added dropwise thereto, drop finishes,
Slowly heating, rises to certain temperature, insulation reaction；
2）, after reaction, reaction solution carries out vacuum distillation recovered solvent, excessive raw material, rectification under vacuum or recrystallization
Refined product.
One kind provided by the invention prepares dimethylaminobenzoic acid ester type compound（Formulas I）Specific steps：
1）, n,N-Dimethylaniline is dissolved in solvent, double (trichloromethyl) carbonic esters are slowly added dropwise thereto, drop finishes,
Slowly heating, rises to certain temperature, insulation reaction；
2）, after the reaction was complete, alcohol is added dropwise, drop finishes, insulation reaction；
3）, after reaction, reaction solution is slowly dropped in water, hydrolysis fully after, stratification, organic phase saturation
Brine It；
4）, the solution after washing is carried out to vacuum distillation recovered solvent, excessive raw material, rectification under vacuum or recrystallization purification
Product.
The preparation method of dimethylaminobenzoic acid ester type compound or dimethylamino chlorobenzoyl chloride provided by the invention, it is special
Sign is step 1）The ratio between amount of the N, accelerine and double (trichloromethyl) carbonic ester materials is selected from 4-15:1.
The preparation method of dimethylaminobenzoic acid ester type compound or dimethylamino chlorobenzoyl chloride provided by the invention, it is special
Sign is step 1）The solvent is selected from chlorobenzene, toluene, dichloroethanes, benzene, dichloromethane.
The preparation method of dimethylaminobenzoic acid ester type compound or dimethylamino chlorobenzoyl chloride provided by the invention, it is special
Sign is step 1）Risen temperature is selected from 40-80 DEG C.
The preparation method of dimethylaminobenzoic acid ester type compound provided by the invention, it is characterised in that step 2）Described
Reaction temperature is selected from -20-60 DEG C.
The alcohol that the present invention is prepared used in dimethylaminobenzoic acid ester type compound is selected from the alcohol containing 1-8 carbon atom, including
The alcohol of straight chain and straight chain, such as：Methanol, ethanol, propyl alcohol, butanol, n-amyl alcohol, isoamyl alcohol, neopentyl alcohol, n-hexyl alcohol, 2- hexanols, 3-
Hexanol, 3- methyl-1-pentenes alcohol, 3- methyl -2- amylalcohols, 3- methyl -3- amylalcohols, normal heptane, positive isooctanol etc..
Dimethylaminobenzoic acid ester type compound prepared by the present invention is 2- dimethylaminobenzoic acids ester type compound and 4-
Dimethylaminobenzoic acid ester type compound.Dimethylamino chlorobenzoyl chloride prepared by the present invention is 2- dimethylaminos chlorobenzoyl chloride and 4-
Dimethylamino chlorobenzoyl chloride.
Dimethylaminobenzoic acid ester type compound and dimethylamino chlorobenzoyl chloride prepared by the present invention can adjust reaction bar
Part（Such as reaction temperature, reaction time）Obtain dimethylaminobenzoic acid ester type compound based on 2- or 4- products and
Dimethylamino chlorobenzoyl chloride product, and 2- can pass through rectification under vacuum or recrystallization progress separating-purifying with 4- products.
The preparation method of dimethylamino chlorobenzoyl chloride provided by the invention is with N, accelerine and double (three chloromethanes
Base) carbonic ester is raw material, is reacted to obtain under gentle reaction condition, purification obtains dimethylamino chlorobenzoyl chloride product；
The preparation of dimethylaminobenzoic acid ester type compound be with N, accelerine and double (trichloromethyl) carbonic esters for raw material into
Row reaction, after the reaction was complete, is not required to purify intermediate, is directly reacted with alcohol, product is obtained by post processing.This preparation
The raw material that method uses is cheap and easy to get and safe, and reaction condition is gently easily-controllable, the system of dimethylaminobenzoic acid ester type compound
Standby process is not required to purify intermediate, can successive reaction.Dangerous small in operating process, operation is fairly simple, reaction knot
Shu Hou, reaction solution is through distillation, rectifying or the product for being recrystallized to give qualification.This method is not only environmental-friendly, but also can reduce
Production cost.
Specific embodiment
In order to illustrate more clearly of the present invention, hereinafter nonlimiting examples are taken to be described further.
Embodiment 1：Preparation to dimethylamino chlorobenzoyl chloride
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（72.7g 0.6mol）It is equal with 30ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 60ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 65 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, drop
To room temperature, vacuum distillation recycling chlorobenzene, chlorobenzene have recycled after first normal pressure, recycle excess raw material n,N-Dimethylaniline, finally subtract
Pressure rectifying obtains product 33.1g and (collects the condition of cut：175~180 DEG C/15mm Hg), yield 60%, purity 99.0%.
Embodiment 2：Preparation to dimethylamino chlorobenzoyl chloride
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（121.2g, 1.0mol）It is equal with 60ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 120ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 65 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, drop
To room temperature, vacuum distillation recycling chlorobenzene, chlorobenzene have recycled after first normal pressure, recycle excess raw material n,N-Dimethylaniline, finally subtract
Pressure rectifying obtains product 44.1g and (collects the condition of cut：175~180 DEG C/15mm Hg), yield 80%, purity 99.1%.
Embodiment 3：The preparation of adjacent dimethylamino chlorobenzoyl chloride
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（121.2g, 1.0mol）It is equal with 60ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 120ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 40 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, gas
Adjacent dimethylamino chlorobenzoyl chloride in phase Chromatogram display reaction solution：It is 75 to dimethylamino chlorobenzoyl chloride：25, recycle solvent and mistake
Content of starting materials, can purify adjacent dimethylamino chlorobenzoyl chloride by rectification under vacuum.
Embodiment 4：The preparation of p-(dimethylamino)-benzoic acid methyl esters
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（121.2g, 1.0mol）It is equal with 60ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 120ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 65 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, drop
To temperature to 30 DEG C, 12.8g absolute methanols are slowly added dropwise, drop finishes, insulation reaction, and TLC or GC monitoring reactions, reaction terminate
Afterwards, during slowly reaction solution is put into 150ml water, stirring hydrolysis, and temperature is controlled at 25 DEG C or so, after 1h, stand and divide
Layer, organic phase saturated common salt water washing, is dried, vacuum distillation recovered solvent and excess raw material with anhydrous sodium sulfate, then is carried out
Rectification under vacuum purification p-(dimethylamino)-benzoic acid methyl esters 43.0g (collects the condition of cut：101~105 DEG C/0.05mm Hg),
Yield 80%, purity 99.2%.
Embodiment 5：The preparation of (dimethylamino)-ethyl benzoate
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（121.2g, 1.0mol）It is equal with 60ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 120ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 65 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, drop
To temperature to 30 DEG C, 18.4g absolute ethyl alcohols are slowly added dropwise, drop finishes, insulation reaction, and TLC or GC monitoring reactions, reaction terminate
Afterwards, slowly reaction solution is put into 150ml water, stirring hydrolysis, and controls temperature at 25 DEG C or so, after 1h, stratification,
Organic phase saturated common salt water washing, is dried with anhydrous sodium sulfate, vacuum distillation recovered solvent and excess raw material, then is depressurized
Rectification and purification (dimethylamino)-ethyl benzoate 47.2g (collects the condition of cut：110~115 DEG C/0.02mm Hg), yield
81%, purity 99.3%.
Embodiment 6：The preparation of isoamyl p-dimethylaminobenzoate
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（121.2g, 1.0mol）It is equal with 60ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 120ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 60 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, drop
To temperature to 30 DEG C, 35.3g isoamyl alcohol is slowly added dropwise, drop finishes, insulation reaction, TLC or GC monitoring reactions, after reaction,
Slowly reaction solution is put into 150ml water, stirring hydrolysis, and controls temperature after 1h, stratification is organic at 25 DEG C or so
Saturated common salt water washing mutually is used, is dried with anhydrous sodium sulfate, vacuum distillation recovered solvent and excess raw material, then carry out rectification under vacuum
Purify isoamyl p-dimethylaminobenzoate 55.8g and (collect the condition of cut：150~155 DEG C/2.5mm Hg), yield
79%, purity 99.5%.
Embodiment 7：The preparation of isooctyl p-dimethylaminobenzoate
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（121.2g, 1.0mol）It is equal with 60ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 120ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 60 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, drop
To temperature to 30 DEG C, 35.3g isoamyl alcohol is slowly added dropwise, drop finishes, insulation reaction, TLC or GC monitoring reactions, after reaction,
Slowly reaction solution is put into 150ml water, stirring hydrolysis, and controls temperature after 1h, stratification is organic at 25 DEG C or so
Saturated common salt water washing mutually is used, is dried with anhydrous sodium sulfate, vacuum distillation recovered solvent and excess raw material, then carry out rectification under vacuum
Purify isoamyl p-dimethylaminobenzoate 62.4g and (collect the condition of cut：200~205 DEG C/3mm Hg), yield 75%,
Purity 99.8%.
Embodiment 8：The preparation of adjacent dimethyl ethyl aminobenzoate
In the four-hole bottle of 500ml, n,N-Dimethylaniline is added（121.2g, 1.0mol）It is equal with 60ml chlorobenzenes, stirring
It is even, will double (trichloromethyl) carbonic esters（29.7g 0.1mol）It is dissolved in 120ml chlorobenzenes, is slowly dropped to n,N-Dimethylaniline
Chlorobenzene solution in, 2h drops finish, and are then to slowly warm up to 40 DEG C, insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, drop
To temperature to 30 DEG C, 18.4g absolute ethyl alcohols are slowly added dropwise, drop finishes, insulation reaction, and TLC or GC monitoring reactions, reaction terminate
Afterwards, slowly reaction solution is put into 150ml water, stirring hydrolysis, and controls temperature at 25 DEG C or so, after 1h, stratification,
Organic phase saturated common salt water washing, is dried with anhydrous sodium sulfate, and gas-chromatography shows adjacent dimethylaminobenzoic acid in organic phase
Ethyl ester：(dimethylamino)-ethyl benzoate is 77：23, vacuum distillation recovered solvent and excess raw material, then carry out rectification under vacuum and carry
The different ethyl ester ester 34.9g of pure neighbour's dimethylaminobenzoic acid (collects the condition of cut：125~130 DEG C/3mm Hg), yield 60%,
Purity 98.8%.
Claims (7)
- A kind of 1. preparation method of 4- dimethylaminos chlorobenzoyl chloride, it is characterised in that including specific steps：At four mouthfuls of 500ml In bottle, 72.7g n,N-Dimethylaniline and 30ml chlorobenzenes are added, is stirred evenly, double (trichloromethyl) carbonic esters of 29.7g are molten In 60ml chlorobenzenes, it is slowly dropped in the chlorobenzene solution of n,N-Dimethylaniline, 2h drops finish, and are then to slowly warm up to 65 DEG C, Insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, are down to room temperature, recycling chlorobenzene are evaporated under reduced pressure after first normal pressure, chlorobenzene returns Harvest, recycle excess raw material n,N-Dimethylaniline, last rectification under vacuum obtains product 33.1g, collects the condition of cut：175 ~180 DEG C/15mm Hg, yield 60%, purity 99.0%.
- A kind of 2. preparation method of 4- dimethylaminos chlorobenzoyl chloride, it is characterised in that including specific steps：At four mouthfuls of 500ml In bottle, 121.2g n,N-Dimethylaniline and 60ml chlorobenzenes are added, is stirred evenly, double (trichloromethyl) carbonic esters of 29.7g are molten In 120ml chlorobenzenes, it is slowly dropped in the chlorobenzene solution of n,N-Dimethylaniline, 2h drops finish, and are then to slowly warm up to 65 DEG C, Insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, are down to room temperature, recycling chlorobenzene are evaporated under reduced pressure after first normal pressure, chlorobenzene returns Harvest, recycle excess raw material n,N-Dimethylaniline, last rectification under vacuum obtains product 44.1g, collects the condition of cut：175 ~180 DEG C/15mm Hg, yield 80%, purity 99.1%.
- A kind of 3. preparation method of 4- dimethylaminobenzoic acids methyl esters, it is characterised in that including specific steps：The four of 500ml In mouth bottle, 121.2g n,N-Dimethylaniline and 60ml chlorobenzenes are added, is stirred evenly, by double (trichloromethyl) carbonic esters of 29.7g It is dissolved in 120ml chlorobenzenes, is slowly dropped in the chlorobenzene solution of n,N-Dimethylaniline, 2h drops finishes, and are then to slowly warm up to 65 DEG C, insulation reaction, TLC or GC monitorings are reacted, and after the reaction was complete, are down to temperature to 30 DEG C, 12.8g absolute methanols are slowly added dropwise, Drop finishes, insulation reaction, and reaction solution, after reaction, is slowly put into 150ml water, stirs water by TLC or GC monitoring reactions Solution, and temperature is controlled at 25 DEG C or so, after 1h, stratification, organic phase saturated common salt water washing, is done with anhydrous sodium sulfate It is dry, vacuum distillation recovered solvent and excess raw material, then rectification under vacuum purification 4- dimethylaminobenzoic acid methyl esters 43.0g are carried out, receive Collect the condition of cut：101~105 DEG C/0.05mm Hg, yield 80%, purity 99.2%.
- A kind of 4. preparation of 4- dimethyl ethyl aminobenzoates, it is characterised in that including specific steps：In the four-hole bottle of 500ml In, 121.2g n,N-Dimethylaniline and 60ml chlorobenzenes are added, is stirred evenly, double (trichloromethyl) carbonic esters of 29.7g are dissolved in In 120ml chlorobenzenes, it is slowly dropped in the chlorobenzene solution of n,N-Dimethylaniline, 2h drops finish, and are then to slowly warm up to 65 DEG C, protect Temperature reaction, TLC or GC monitoring reactions, after the reaction was complete, are down to temperature to 30 DEG C, 18.4g absolute ethyl alcohols are slowly added dropwise, and drop finishes, Reaction solution, after reaction, is slowly put into 150ml water, stirring hydrolysis, and control by insulation reaction, TLC or GC monitoring reactions Temperature processed is at 25 DEG C or so, and after 1h, stratification, organic phase saturated common salt water washing, is dried with anhydrous sodium sulfate, and decompression is steamed Recycling design and excess raw material are evaporated, then carries out rectification under vacuum purification 4- dimethyl ethyl aminobenzoate 47.2g, collects the bar of cut Part：110~115 DEG C/0.02mm Hg, yield 81%, purity 99.3%.
- A kind of 5. preparation of 4- dimethylaminobenzoic acids isopentyl ester, it is characterised in that including specific steps：At four mouthfuls of 500ml In bottle, 121.2g n,N-Dimethylaniline and 60ml chlorobenzenes are added, is stirred evenly, double (trichloromethyl) carbonic esters of 29.7g are molten In 120ml chlorobenzenes, it is slowly dropped in the chlorobenzene solution of n,N-Dimethylaniline, 2h drops finish, and are then to slowly warm up to 60 DEG C, Insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, are down to temperature to 30 DEG C, 35.3g isoamyl alcohol are slowly added dropwise, and drop finishes, Reaction solution, after reaction, is slowly put into 150ml water, stirring hydrolysis, and control by insulation reaction, TLC or GC monitoring reactions Temperature processed is at 25 DEG C or so, and after 1h, stratification, organic phase saturated common salt water washing, is dried with anhydrous sodium sulfate, and decompression is steamed Recycling design and excess raw material are evaporated, then carries out rectification under vacuum purification 4- dimethylaminobenzoic acid isopentyl ester 55.8g, collects cut Condition：150~155 DEG C/2.5mm Hg, yield 79%, purity 99.5%.
- A kind of 6. preparation of the different monooctyl ester of 4- dimethylaminobenzoic acids, it is characterised in that including specific steps：At four mouthfuls of 500ml In bottle, 121.2g n,N-Dimethylaniline and 60ml chlorobenzenes are added, is stirred evenly, double (trichloromethyl) carbonic esters of 29.7g are molten In 120ml chlorobenzenes, it is slowly dropped in the chlorobenzene solution of n,N-Dimethylaniline, 2h drops finish, and are then to slowly warm up to 60 DEG C, Insulation reaction, TLC or GC monitoring reactions, after the reaction was complete, are down to temperature to 30 DEG C, 35.3g isoamyl alcohol are slowly added dropwise, and drop finishes, Reaction solution, after reaction, is slowly put into 150ml water, stirring hydrolysis, and control by insulation reaction, TLC or GC monitoring reactions Temperature processed is at 25 DEG C or so, and after 1h, stratification, organic phase saturated common salt water washing, is dried with anhydrous sodium sulfate, and decompression is steamed Recycling design and excess raw material are evaporated, then carries out the rectification under vacuum purification different monooctyl ester 62.4g of 4- dimethylaminobenzoic acids, collects cut Condition：200~205 DEG C/3mm Hg, yield 75%, purity 99.8%.
- A kind of 7. preparation of 2- dimethyl ethyl aminobenzoates, it is characterised in that including specific steps：In the four-hole bottle of 500ml In, 121.2g n,N-Dimethylaniline and 60ml chlorobenzenes are added, is stirred evenly, double (trichloromethyl) carbonic esters of 29.7g are dissolved in In 120ml chlorobenzenes, it is slowly dropped in the chlorobenzene solution of n,N-Dimethylaniline, 2h drops finish, and are then to slowly warm up to 40 DEG C, protect Temperature reaction, TLC or GC monitoring reactions, after the reaction was complete, are down to temperature to 30 DEG C, 18.4g absolute ethyl alcohols are slowly added dropwise, and drop finishes, Reaction solution, after reaction, is slowly put into 150ml water, stirring hydrolysis, and control by insulation reaction, TLC or GC monitoring reactions Temperature processed is at 25 DEG C or so, and after 1h, stratification, organic phase saturated common salt water washing, is dried, gas phase color with anhydrous sodium sulfate Spectrum shows adjacent dimethyl ethyl aminobenzoate in organic phase：(dimethylamino)-ethyl benzoate is 77：23, vacuum distillation recycling is molten Agent and excess raw material, then rectification under vacuum purification 2- dimethyl ethyl aminobenzoate 34.9g are carried out, collect the condition of cut：125~ 130 DEG C/3mm Hg, yield 60%, purity 98.8%.
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| US2882472A (en) * | 1955-11-02 | 1959-04-14 | Sprague Electric Co | Electrical capacitors |
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| US2882472A (en) * | 1955-11-02 | 1959-04-14 | Sprague Electric Co | Electrical capacitors |
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| "三光气的反应机理和应用";季宝等;《科技情报开发与经济》;20091231;第19卷(第10期);136-137 * |
| "对氨基苯甲酸酯类的紫外吸收性能的定量构效关系Ⅰ化合物的合成及其PPP法量子化学计算";缪裘缇等;《华东化工学院学报》;19921031;第18卷(第5期);634-640 * |
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