CN101863791A - Method for synthesizing 2-Ethylhexyl p-dimethylaminobenzoate (EHA) - Google Patents
Method for synthesizing 2-Ethylhexyl p-dimethylaminobenzoate (EHA) Download PDFInfo
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- CN101863791A CN101863791A CN201010209076A CN201010209076A CN101863791A CN 101863791 A CN101863791 A CN 101863791A CN 201010209076 A CN201010209076 A CN 201010209076A CN 201010209076 A CN201010209076 A CN 201010209076A CN 101863791 A CN101863791 A CN 101863791A
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- benzoic acid
- dimethylamino
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- eha
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- 238000000034 method Methods 0.000 title claims abstract description 22
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 title abstract 6
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 24
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- -1 halogeno benzene benzoic acid Chemical compound 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 claims description 27
- 150000002148 esters Chemical class 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000010189 synthetic method Methods 0.000 claims description 9
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000012044 organic layer Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 5
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 claims description 2
- 101150116295 CAT2 gene Proteins 0.000 claims description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 claims description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 208000012839 conversion disease Diseases 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- UMVOQQDNEYOJOK-UHFFFAOYSA-N 3,5-dimethylbenzoic acid Chemical compound CC1=CC(C)=CC(C(O)=O)=C1 UMVOQQDNEYOJOK-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001035 methylating effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N 2-(dimethylamino)-1-phenylethanone Chemical compound CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DBQGARDMYOMOOS-UHFFFAOYSA-N methyl 4-(dimethylamino)benzoate Chemical class COC(=O)C1=CC=C(N(C)C)C=C1 DBQGARDMYOMOOS-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- SCNYCWQULCHALD-UHFFFAOYSA-N propyl 4-(dimethylamino)benzoate Chemical compound CCCOC(=O)C1=CC=C(N(C)C)C=C1 SCNYCWQULCHALD-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing 2-Ethylhexyl p-dimethylaminobenzoate (EHA) and production technology research thereof. The method comprises the steps of: reacting halogeno benzene benzoic acid as raw materials with dimethylamine and isooctanol, removing a solvent and isooctanol via reduced pressure distillation to obtain the 2-Ethylhexyl p-dimethylaminobenzoate (EHA), wherein the product has the purity being greater than 98% and the overall yield being 85%. The process has the characteristics of mild reaction condition, simple operation, environmental protection and easy recycling of the solvent, and is suitable for industrial production.
Description
Invention field
The present invention relates to the synthetic method and the production technique of a kind of important different monooctyl ester of ultraviolet initiator p-(dimethylamino)-benzoic acid of chemical industry.Method of the present invention is to be raw material to halogenated benzoic acid, through reacting with dimethylamine, reacts with isooctyl alcohol in the presence of catalyzer again, remove through underpressure distillation then and desolvate and isooctyl alcohol, obtain the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA), product purity is greater than 99%, and total recovery is more than 85%.Synthetic method of the present invention has from basic chemical raw materials, and no severe condition are simple to operate, environmentally friendly, solvent easy to recovery of applied etc. characteristics, be fit to be applied to industrial production.
Background of invention
The p-(dimethylamino)-benzoic acid ester series compound is a class amine promoter efficiently, same free radical (II) type light trigger uses together, the varnish colour system that is mainly used in paper, timber, metal and frosting is carried out ultra-violet curing, also can be used for single or multiple monomeric ultraviolet radiation polyreaction, or the sensitizing agent of excellent property, normal and thioxanthone photoinitiator, acetophenones light trigger are united use, photoinitiation can be promoted, the interference effect of oxygen can be effectively eliminated again light initiation polymerization.
The p-(dimethylamino)-benzoic acid ester series compound, can do good uvioresistant additive, be widely used in the water-fast sun care preparations, comprising p-(dimethylamino)-benzoic acid isopentyl ester (IADB) and the different monooctyl ester (EHA of p-(dimethylamino)-benzoic acid, commodity by name 507), the latter is a kind of UV light absorber of good UVB district, as sun-screening agent, used in large quantities in the world, U.S. FDA is classified it as sun-screening agent that the first kind is recommended use.The p-(dimethylamino)-benzoic acid ester not only is applied to cosmetic field, and also can be used as sanitas and use, as: p-(dimethylamino)-benzoic acid methyl esters, p-(dimethylamino)-benzoic acid propyl ester, the positive butyl ester of p-(dimethylamino)-benzoic acid and solution thereof all have preservative activity.
The processing method of existing synthetic p-(dimethylamino)-benzoic acid ester, usually all be substrate with the p-(dimethylamino)-benzoic acid, therefore seek the synthetic method of a suitable p-(dimethylamino)-benzoic acid suitability for industrialized production, crucial meaning is arranged for exploitation p-(dimethylamino)-benzoic acid derivatives class series product.
The main method of at present synthetic p-(dimethylamino)-benzoic acid has: (1) is to carboxylated (Journal of Organic Chemistry, 55 (6), the 1768-71 of dimethylamino halogeno-benzene; 1990); (2) carboxylated to the haloform of dimethylamino methyl phenyl ketone; (3) nitrogen of the para-amino benzoic acid (GB2233975 that methylates; Huaxue Shiji, 25 (4), 245-246; 2003; Journal of Organic Chemistry, 70 (7), 2476-2485; 2005); (4) direct oxidation of paradimethy laminobenzaldehyde (Organic Letters, 9 (18), 3515-3518; 2007; Huaihai Gongxueyuan Xuebao, ziran Kexueban, 14 (2), 53-55; 2005).Method (1), (2) and (3) are not suitable for large-scale industrial production owing to raw materials cost height, toxicity are big, the uneasy congruent factor of operation, and wherein method (3) also can produce the by product of a large amount of monomethylations, brings difficulty for product separation and purifying; Method (4) is the classical way that aromatic aldehyde is oxidized to aromatic carboxylic acid, but the cost of aromatic aldehyde is higher, and oxidation step often need use the active Textone of expensive Silver Nitrate and character, is not suitable for big industrial production.
Diformazan aminobenzoic acid ester preparation method there be (I) to the direct esterification of diformazan aminobenzoic acid (Journal of Organic Chemistry, 70 (7), 2476-2485; 2005; ); (I I) vitamin Bx ester methylates through formaldehyde catalysis nitrogen, and (GB 2233975; CN1289764).Shortcomings such as method (I) exists the p-(dimethylamino)-benzoic acid cost more expensive, and esterification yield is low, and the acid waste water amount is big.It is fully very difficult that method (II) exists nitrogen to methylate, and used methylating reagent methyl-sulfate toxicity is big, the acid waste water amount is many; With methyl chloride, methyl iodide cost height, both exist simultaneously, and ester has partial hydrolysis in the process of methylating, and influences the productive rate shortcoming.
Summary of the invention
The objective of the invention is to overcome the existing existing shortcoming of synthetic method, provide that a kind of operational path is short, raw material is easy to get, condition is gentle, easy and simple to handle relatively, the three wastes are few, the synthetic method of the different monooctyl ester of the p-(dimethylamino)-benzoic acid of high yield (EHA).This method adopt domestic be easy to get halogenated benzoic acid and dimethylamine agueous solution are done raw material, catalyzer exist down ammonia separate, again through catalytic esterification, the different monooctyl ester of the p-(dimethylamino)-benzoic acid of the synthetic high level of high yield (EHA).All steps do not have severe condition, and are simple to operate, environmentally friendly, meet requirements of green environmental protection, have remarkable social benefit and economic benefit, are fit to suitability for industrialized production.
The structural formula of the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA) is as follows:
For achieving the above object, the step that comprises of synthetic method provided by the invention: its synthesis step is:
X＝Cl，Br
The concrete operations step is as follows:
Step 1: be under 10～150 ℃ the condition in temperature, in to the mixed system of halogenated benzoic acid and dimethylamine agueous solution, add catalyzer Cat-1, and 50～200 ℃ of heated and stirred 5～20 hours, be cooled to room temperature, behind the reacting liquid filtering, filtrate is regulated pH ≈ 4 with dilute hydrochloric acid, filters the solid crude product that obtains p-(dimethylamino)-benzoic acid, can be directly used in the next step after drying.
In the step 1 of the present invention, the catalyzer Cat-1 of adding is a tetrabutylammonium chloride, Tetrabutyl amonium bromide, trimethyl benzyl ammonia chloride, polyoxyethylene glycol 800～1200, phase-transfer catalysts such as glycerine; Catalyzer Cat-2 is CuCl
2, Cu
2O, Cu powder, CoCl
2This two classes catalyzer makes reaction conditions more gentle when accelerating speed of reaction; Excessive dimethylamine is beneficial to promotion reaction conversion as the acid binding agent of reaction, but and multistep recycled.
Step 2: be under 20～80 ℃ the condition in temperature, in the mixed system of p-(dimethylamino)-benzoic acid, isooctyl alcohol and solvent orange 2 A, add catalyzer Cat-3, be heated to reaction system boiling and through minute fluidization tower extraction solvent and water, treat to keep 1～2 hour again to no longer including the water generation after the material clarification, sampling analysis to feed stock conversion greater than 99%, about 3～15 hours of this process.Reaction system is cooled to room temperature, is neutralized to neutrality, leaves standstill to tell organic layer, and vacuum distillation recovered solvent and remaining isooctyl alcohol continue underpressure distillation again and obtain product.
In the step 2 of the present invention, reaction solvent A can be benzene,toluene,xylene, chlorobenzene and dichlorobenzene, preferred dimethylbenzene; Catalyzer Cat-3 is a tosic acid, sulfuric acid, phosphoric acid, boric acid and tetra-sodium, preferential phosphoric acid; The post processing mode that adopts is: reaction solution is neutralized to neutrality, leaves standstill to tell organic layer, sloughs solvent and residual raw materials, gets the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA), and product purity is greater than 99%; Two step total recoverys are greater than 85%.
The invention relates to the synthetic method of the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA), synthetic route is totally two steps, and is shorter than the additive method step, more help big industrial production, this route does not have obvious by product, the acid binding agent of the dimethylamine double as reaction of one of substrate, but multistep recycled.The present invention can provide the total recovery more than 85%, and product purity is greater than 99%, institute do not have in steps severe condition, simple to operate, environmentally friendly, solvent is easy to recovery of applied, is fit to be applied to industrial production.
Embodiment
In order to be illustrated more clearly in the present invention, hereinafter adopt indefiniteness embodiment to be described further.
Embodiment one
(1) step 1: the preparation of p-(dimethylamino)-benzoic acid
Add 78.0g (0.5mol) Chlorodracylic acid in the autoclave of 2L successively, 1364g (10mol) dimethylamine agueous solution (wt 33%) adds 7.8g CuCl again
22H
2O and 7.8g tetrabutylammonium chloride, temperature of reaction are 150 ℃, heating 15h, monitor to feedstock conversion fully through HPLC, reaction finishes, and dimethylamine is reclaimed in distillation, be cooled to room temperature then, with dilute hydrochloric acid regulation system pH ≈ 4, separate out a large amount of yellow crystals behind the reacting liquid filtering, in ice bath behind the cooling 10min, suction filtration, solid drying gets product 74.7g, single step yield 90.6%, structure warp
1H-NMR, MS conclusive evidence.
(2) step 2: the preparation of the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA)
In the four-hole bottle that installs agitator, thermometer, reflux condensation mode and water trap, add 156.0g (1mol) p-(dimethylamino)-benzoic acid, 143.0g (1.1mol) isooctyl alcohol, 420ml chlorobenzene and 18g phosphoric acid.Heated and stirred is warming up to boiling, the about 8h of reflux water-dividing, treat vial material clarification after, keep the 1～2h that refluxes again, generate to no longer including water, the sampling analysis material content is less than 1.0%, reaction finishes.Be cooled to room temperature, be neutralized to neutrality, leave standstill and tell organic layer, underpressure distillation removes removal xylene and isooctyl alcohol, continue to distill product 264.5g, HPLC purity: 99.3%, single step yield 95.5%, structure warp
1H-NMR, MS conclusive evidence.
Two step total recoverys 86.5%.
Embodiment two
(1) step 1: the preparation of p-(dimethylamino)-benzoic acid
Add 100.0g (0.5mol) parabromobenzoic acid in the autoclave of 2L successively, 1364g (10mol) dimethylamine agueous solution (wt 33%) adds 8.8g CuCl again
22H
2O and 7.8g tetrabutylammonium chloride, temperature of reaction are 150 ℃, heating 15h, monitor to feedstock conversion fully through HPLC, reaction finishes, and dimethylamine is reclaimed in distillation, be cooled to room temperature then, with dilute hydrochloric acid regulation system pH ≈ 4, separate out a large amount of yellow crystals behind the reacting liquid filtering, in ice bath behind the cooling 10min, suction filtration, solid drying gets product 78.8g, single step yield 95.6%, structure warp
1H-NMR, MS conclusive evidence.
(2) step 2: the preparation of the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA)
In the reactor that installs agitator, thermometer, reflux condensation mode and water trap (four-hole bottle), add 165.0g (1mol) p-(dimethylamino)-benzoic acid, 143.0g (1.1mol) isooctyl alcohol, 420ml dimethylbenzene and 5g sulfuric acid (wt 98% content).Heated and stirred is warming up to boiling, the about 8h of reflux water-dividing, treat vial material clarification after, keep the 1～2h that refluxes again, generate to no longer including water, the sampling analysis material content is less than 1.0%, reaction finishes.Be cooled to room temperature, be neutralized to neutrality, leave standstill and tell organic layer, underpressure distillation removes removal xylene and isooctyl alcohol, continue to distill product 270g, HPLC purity: 99.3%, single step yield 95.5%, structure warp
1H-NMR, MS conclusive evidence.
Two step total recoverys 91.3%.
Claims (4)
1. the synthetic method of the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA), described method comprises following two steps:
Step 1: be under 10～150 ℃ the condition in temperature, in to the mixed system of halogenated benzoic acid and dimethylamine agueous solution, add catalyzer Cat-1, and 50～200 ℃ of heated and stirred 5～20 hours, be cooled to room temperature, behind the reacting liquid filtering, filtrate is regulated pH ≈ 4 with dilute hydrochloric acid, filters the solid crude product that obtains p-(dimethylamino)-benzoic acid, can be directly used in the next step after drying.
Step 2: be under 20～80 ℃ the condition in temperature, in the mixed system of p-(dimethylamino)-benzoic acid, isooctyl alcohol and solvent orange 2 A, add catalyzer Cat-3, be heated to reaction system boiling and through minute fluidization tower extraction solvent and water, treat to keep 1～2 hour again to no longer including the water generation after the material clarification, sampling analysis to feed stock conversion greater than 99%, about 3～15 hours of this process.Reaction system is cooled to room temperature, is neutralized to neutrality, leaves standstill to tell organic layer, and vacuum distillation recovered solvent and remaining isooctyl alcohol continue underpressure distillation again and obtain product.
2. according to the method for claim 1, it is characterized in that in the described step 1 that inventing a kind of is the method for feedstock production to mesitylenic acid with facile halogenated benzoic acid.
3. according to the method for claim 1, it is characterized in that in the described step 1 that having introduced catalysts Cat-1 is tetrabutylammonium chloride, Tetrabutyl amonium bromide, trimethyl benzyl ammonia chloride, polyoxyethylene glycol 800～1200, phase-transfer catalysts such as glycerine; Catalyzer Cat-2 is CuCl
2, Cu
2O, Cu powder, CoCl
2This two classes catalyzer makes reaction conditions more gentle when accelerating speed of reaction; Excessive dimethylamine is beneficial to promotion reaction conversion as the acid binding agent of reaction, but and multistep recycled.
4. according to the method for claim 1, it is characterized in that in the described step 2, solvent orange 2 A is benzene,toluene,xylene, chlorobenzene and dichlorobenzene, is preferably dimethylbenzene; Reaction is preferably at 80～150 ℃; Catalyzer Ca t-3 is a tosic acid, sulfuric acid, phosphoric acid, boric acid and tetra-sodium, preferential phosphoric acid; The post processing mode that adopts is: reaction solution is neutralized to neutrality, leaves standstill to tell organic layer, sloughs solvent and residual raw materials, gets the different monooctyl ester of p-(dimethylamino)-benzoic acid (EHA).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746172A (en) * | 2012-06-25 | 2012-10-24 | 湖北远成药业有限公司 | Preparation method of dimethylaminocinnamaldehyde |
| CN107935817A (en) * | 2017-12-12 | 2018-04-20 | 浙江优创材料科技股份有限公司 | Isooctyl p-dimethylaminobenzoate crude product recycles the devices and methods therefor of isooctanol |
| CN108546232A (en) * | 2018-05-22 | 2018-09-18 | 湖北汇达科技发展有限公司 | A kind of monosubstituted or disubstituted benzene formic ether compounds preparation methods |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070017151A1 (en) * | 2005-07-22 | 2007-01-25 | National Taiwan Normal University | Nucleophilic Acyl Substitutions of Acids or Esters Catalyzed by Oxometallic Complexes, and the Applications in Fabricating Biodiesel |
-
2010
- 2010-06-25 CN CN2010102090767A patent/CN101863791B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070017151A1 (en) * | 2005-07-22 | 2007-01-25 | National Taiwan Normal University | Nucleophilic Acyl Substitutions of Acids or Esters Catalyzed by Oxometallic Complexes, and the Applications in Fabricating Biodiesel |
Non-Patent Citations (5)
| Title |
|---|
| C. VILLA, ET AL.: "Eco-friendly methodologies for the synthesis of some aromatic esters, well-known cosmetic ingredients", 《INTERNATIONAL JOURNAL OF COSMETIC SCIENCE》 * |
| JOHN T. GUPTON, ET AL.: "Reaction of Activated Aryl and Heteroaryl Halides with Hexamethylphosphoramide", 《J. ORG. CHEM.》 * |
| PHILIP J. SKINNER， ET AL.: "3-Nitro-4-amino benzoic acids and 6-amino nicotinic acids are highly selective agonists of GPR109b", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
| 彭梦侠等: "对二甲氨基苯甲酸异辛酯的合成研究", 《化工时刊》 * |
| 杨运旭: "紫外线吸收剂Padimate O 的合成研究", 《化学世界》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746172A (en) * | 2012-06-25 | 2012-10-24 | 湖北远成药业有限公司 | Preparation method of dimethylaminocinnamaldehyde |
| CN102746172B (en) * | 2012-06-25 | 2014-07-30 | 湖北远成赛创科技有限公司 | Preparation method of dimethylaminocinnamaldehyde |
| CN107935817A (en) * | 2017-12-12 | 2018-04-20 | 浙江优创材料科技股份有限公司 | Isooctyl p-dimethylaminobenzoate crude product recycles the devices and methods therefor of isooctanol |
| CN107935817B (en) * | 2017-12-12 | 2023-08-29 | 浙江优创材料科技股份有限公司 | Device and method for recovering isooctyl alcohol from isooctyl p-dimethylaminobenzoate crude product |
| CN108546232A (en) * | 2018-05-22 | 2018-09-18 | 湖北汇达科技发展有限公司 | A kind of monosubstituted or disubstituted benzene formic ether compounds preparation methods |
| CN108546232B (en) * | 2018-05-22 | 2020-10-16 | 湖北汇达科技发展有限公司 | Preparation method of mono-substituted or di-substituted benzoate compound |
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