CN105367436A - Preparation method of N,N-dimethyl benzoate composite - Google Patents
Preparation method of N,N-dimethyl benzoate composite Download PDFInfo
- Publication number
- CN105367436A CN105367436A CN201410426414.0A CN201410426414A CN105367436A CN 105367436 A CN105367436 A CN 105367436A CN 201410426414 A CN201410426414 A CN 201410426414A CN 105367436 A CN105367436 A CN 105367436A
- Authority
- CN
- China
- Prior art keywords
- preparation
- reaction
- trichloromethyl
- drip
- dma
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 60
- -1 dimethylaminobenzoic acid ester compound Chemical class 0.000 claims description 32
- TWAOVIVEUFBAHK-UHFFFAOYSA-N 2-(dimethylamino)benzoyl chloride Chemical compound CN(C)C1=CC=CC=C1C(Cl)=O TWAOVIVEUFBAHK-UHFFFAOYSA-N 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 19
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 18
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005292 vacuum distillation Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 238000013517 stratification Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 238000001953 recrystallisation Methods 0.000 claims description 6
- LAYPMCGIWDGYKX-UHFFFAOYSA-N trichloromethyl hydrogen carbonate Chemical compound OC(=O)OC(Cl)(Cl)Cl LAYPMCGIWDGYKX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 abstract 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000010792 warming Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- KJSGODDTWRXQRH-UHFFFAOYSA-N 2-(dimethylamino)ethyl benzoate Chemical compound CN(C)CCOC(=O)C1=CC=CC=C1 KJSGODDTWRXQRH-UHFFFAOYSA-N 0.000 description 4
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229960005274 benzocaine Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 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 4
- 238000000746 purification Methods 0.000 description 4
- DVVXXHVHGGWWPE-UHFFFAOYSA-N 2-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=CC=C1C(O)=O DVVXXHVHGGWWPE-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver nitrate Substances [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000003254 radicals Chemical class 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SKYBRLALUDNCSM-UHFFFAOYSA-N 1,1-dimethyl-2-phenylhydrazine Chemical compound CN(C)NC1=CC=CC=C1 SKYBRLALUDNCSM-UHFFFAOYSA-N 0.000 description 1
- AQFXIWDRLHRFIC-UHFFFAOYSA-N 1-[5-phenyl-3-(trifluoromethyl)pyrazol-1-yl]ethanone Chemical compound CC(=O)N1N=C(C(F)(F)F)C=C1C1=CC=CC=C1 AQFXIWDRLHRFIC-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-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
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- UAKWLVYMKBWHMX-UHFFFAOYSA-N SU4312 Chemical compound C1=CC(N(C)C)=CC=C1C=C1C2=CC=CC=C2NC1=O UAKWLVYMKBWHMX-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002473 indoazoles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of an N,N-dimethyl benzoate composite, in particular to a preparation method for preparing N,N-dimethyl benzoate by using N,N-dimethylaniline, bi(trichloromethyl)carbonic ester and alcohol as raw materials. The raw materials are cheap and easy to obtain, the yield is high, a midbody does not need to be purified, a continuous reaction can be performed without replacing solvents, the preparation method is cheap, environmentally friendly, easy to implement and suitable for industrialization, and the method can be used for preparing the important chemical and medical midbody through N,N-dimethyl benzoyl chloride.
Description
Technical field
The present invention relates to a kind of N, the preparation method of N-mesitylenic acid ester compound, be specifically related to N, accelerine, two (trichloromethyl) carbonic ether and alcohol are that N prepared by raw material, the preparation method of N-mesitylenic acid ester, present method cheaper starting materials is easy to get, yield is high, and intermediate does not need to purify, not needing to change solvent can successive reaction, is the preparation method of a kind of cheapness, environmental protection, easy to operate, suitability for industrialized.And utilize present method to prepare N, the chemical industry that N-dimethyl benzoyl chloride is important and medicine intermediate.
Background technology
Dimethylaminobenzoic acid ester compound is the organism that a class has extensive use, is conventional organic bases, phase-transfer catalyst, amine promoter, sterilant, sanitas, sun-screening agent, fine-chemical intermediate, medicine intermediate etc.P-(dimethylamino)-benzoic acid ester compound is the efficient amine promoter of a class, same free radical (II) type light trigger uses together, and ultraviolet light polymerization is carried out in the aspect such as varnish colour system, ink, tackiness agent being widely used in paper, timber, metal and frosting; Ultraviolet radiation polyreaction that is single or various of monomer can also be used for, but also be good sensitizing agent, normal and other light trigger conbined usage, as: thioxanthones, acetophenones light trigger, can photoinitiation be promoted, effectively can eliminate again the interference effect that oxygen is polymerized light trigger.This series compound has a large amount in variety at present, as: (dimethylamino)-ethyl benzoate (EBD), EHA (EHA, commodity by name 507), IADB (DMBI), p-(dimethylamino)-benzoic acid methyl esters, p-(dimethylamino)-benzoic acid propyl ester, the positive butyl ester of p-(dimethylamino)-benzoic acid etc., 2-dimethyl ethyl aminobenzoate.
P-(dimethylamino)-benzoic acid ester series compound is a kind of good UVB district UV light absorber, can also as excellent uvioresistant additive, be widely used in water-fast sun care preparations, wherein EHA is classified as the sun-screening agent of first kind recommendation by U.S. FDA.Meanwhile, p-(dimethylamino)-benzoic acid ester series compound also can use as sanitas, and 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.
Existing p-(dimethylamino)-benzoic acid ester series compound preparation method has three kinds:
1), p-(dimethylamino)-benzoic acid directly carries out esterification, generally makees catalyzer (BioorganicandMedicinalChemistry, 18(22) with acid: 7836-7841; 2010) esterification is carried out with correspondent alcohol;
2), P aminobenzoates carries out nitrogen and methylates, methylated reagent is generally methyl-sulfate (JournaloftheChemicalSociety, ChemicalCommunications, 17:1202-1203,1985), formaldehyde sodium cyanoborohydride (JournaloftheAmericanChemicalSociety, 120(2): 5193 – 5202,1998), methyl iodide (JournalofOrganicChemistry, 75(5): 1378-1385,2010);
3) be, with paradimethy laminobenzaldehyde raw material, catalyst oxidation silver or Silver Nitrate (Huaihai Institute of Technology journal (natural science edition), 14(2): 53-55,2005) effect under be oxidized to p-(dimethylamino)-benzoic acid, then esterification under acid catalysis.Or (TetrahedronLetters under tetrakis triphenylphosphine palladium and benzyl bromine co-catalysis, 52(41): 5319-5322,2011) or 1,2-dimethyl indazole-3-formate (OrganicLetters, 9(18): 3515-3518,2007) obtained p-(dimethylamino)-benzoic acid ester is reacted under catalysis with correspondent alcohol.
Method 1) Problems existing is that the yield of esterification is low, cause production cost higher, but also produce a large amount of acid waste water, environment is unfriendly; Method 2) shortcoming be that nitrogen methylates and is difficult to completely, methyl-sulfate toxicity is comparatively large, and waste water is many, and methyl iodide, the large cost of sodium cyanoborohydride toxicity are high; Method 3) namely avoid the reagent that use toxicity is larger, also acid waste water can not be produced, but be the use of the high precious metal chemical complex of price, tetrakis triphenylphosphine palladium and benzyl bromine catalyst or indazole salt catalyst, catalyzer cost is high and consumption is large, therefore cause whole cost very high, be not suitable for suitability for industrialized production.
2-dimethyl ethyl aminobenzoate not only can be used in photocuring system, and simultaneously or important chemical intermediate and medicine intermediate, it is less that its preparation method is reported at present.Dimethylamino Benzoyl chloride is also very important fine-chemical intermediate and medicine intermediate.The preparation method of dimethylamino Benzoyl chloride is generally be raw material by dimethylaminobenzoic acid, by preparing with highly acid oxalyl chloride, thionyl chloride, phosgene, phosphorus pentachloride back flow reaction, this class methods raw materials cost is high, requires high to reactor, and have acid gas to produce, unfavorable to environment.
Summary of the invention
The object of the invention is to overcome the shortcoming existing for existing preparation method, provide that a kind of cheaper starting materials is easy to get, use safety, reaction conditions gentleness are easy to operate and reach the preparation method of high purity, high yield, few, the eco-friendly dimethylaminobenzoic acid ester compound of the three wastes.The method is with DMA, two (trichloromethyl) carbonic ether and alcohol for raw material, and after DMA and two (trichloromethyl) carbonate reaction, the intermediate obtained carries out alcoholysis; Or obtain dimethylamino Benzoyl chloride intermediate through process later after dimethylamino-aniline and two (trichloromethyl) carbonate reaction, and then carry out alcoholysis and obtain dimethylaminobenzoic acid ester compound.Technique provided by the invention is simple, processing ease, and cost is low, and yield is high, product purity is high, no matter solid product or product liquid, and outward appearance is better, environmentally friendly, meet the requirement of environmental protection, there is significant Social benefit and economic benefit, be applicable to suitability for industrialized production.
In order to achieve the above object, the preparation method of dimethylaminobenzoic acid ester compound provided by the invention take DMA as raw material.Dimethylaminobenzoic acid ester compound and as follows with the structural formula of DMA:
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 provided by the invention prepares dimethylamino Benzoyl chloride (formula III):
By DMA (formula II), under presence or absence organic solvent, prepare with two (trichloromethyl) carbonate reaction.
One provided by the invention prepares dimethylaminobenzoic acid ester compound (formula I):
Wherein, R represents the alkyl of 1-8 carbon atom.
1) by DMA (formula II), under presence or absence organic solvent, with two (trichloromethyl) carbonate reaction; With
2) react with alcohol subsequently;
The method need not isolation of intermediate products dimethylamino Benzoyl chloride.
One provided by the invention prepares the concrete steps of dimethylamino Benzoyl chloride (formula III):
1), by DMA be dissolved in solvent, slowly drip two (trichloromethyl) carbonic ether wherein, drip and finish, slowly heat up, rise to certain temperature, insulation reaction;
2), reaction terminate after, reaction solution carries out vacuum distillation recovered solvent, excessive raw material, rectification under vacuum or recrystallization refined product.
One provided by the invention prepares dimethylaminobenzoic acid ester compound (formula I) concrete steps:
1), by DMA be dissolved in solvent, slowly drip two (trichloromethyl) carbonic ether wherein, drip and finish, slowly heat up, rise to certain temperature, insulation reaction;
2), react completely after, drip alcohol, drip finish, insulation reaction;
3), after reaction terminates, reaction solution is slowly added drop-wise in water, after hydrolysis fully, stratification, organic phase saturated common salt water washing;
4), the solution after washing is carried out vacuum distillation recovered solvent, excessive raw material, rectification under vacuum or recrystallization refined product.
The preparation method of dimethylaminobenzoic acid ester compound provided by the invention or dimethylamino Benzoyl chloride, is characterized in that the ratio of DMA described in step 1) and two (trichloromethyl) carbonic ether amount of substance is selected from 4-15:1.
The preparation method of dimethylaminobenzoic acid ester compound provided by the invention or dimethylamino Benzoyl chloride, is characterized in that solvent described in step 1) is selected from chlorobenzene, toluene, ethylene dichloride, benzene, methylene dichloride.
The preparation method of dimethylaminobenzoic acid ester compound provided by the invention or dimethylamino Benzoyl chloride, is characterized in that step 1) degree of intensification is selected from 40-80 DEG C.
The preparation method of dimethylaminobenzoic acid ester compound provided by the invention, is characterized in that step 2) described in temperature of reaction be selected from-20-60 DEG C.
The present invention prepares dimethylaminobenzoic acid ester compound alcohol used and is selected from alcohol containing 1-8 carbon atom, comprise the alcohol of straight chain and straight chain, such as: methyl alcohol, ethanol, propyl alcohol, butanols, Pentyl alcohol, primary isoamyl alcohol, neopentyl alcohol, n-hexyl alcohol, 2-hexanol, 3-hexanol, 3-methyl-1-pentene alcohol, 3-methyl-2-amylalcohol, 3-methyl-3-amylalcohol, normal heptane, positive isooctyl alcohol etc.
Dimethylaminobenzoic acid ester compound prepared by the present invention is 2-dimethylaminobenzoic acid ester compound and 4-dimethylaminobenzoic acid ester compound.Dimethylamino Benzoyl chloride prepared by the present invention is 2-dimethylamino Benzoyl chloride and 4-dimethylamino Benzoyl chloride.
Dimethylaminobenzoic acid ester compound prepared by the present invention and dimethylamino Benzoyl chloride can regulate reaction conditions (such as temperature of reaction, reaction times) to obtain based on the dimethylaminobenzoic acid ester compound of 2-position or 4-position product and dimethylamino Benzoyl chloride product, and 2-position and 4-position product can carry out separating-purifying by rectification under vacuum or recrystallization.
The preparation method of dimethylamino Benzoyl chloride provided by the invention be with DMA and two (trichloromethyl) carbonic ether for raw material, be obtained by reacting under the reaction conditions of gentleness, purify and obtain dimethylamino Benzoyl chloride product; The preparation of dimethylaminobenzoic acid ester compound is that raw material reacts with DMA and two (trichloromethyl) carbonic ether, after reacting completely, do not need to purify to intermediate, directly and alcohol react, obtain product through aftertreatment.The cheaper starting materials that this preparation method uses is easy to get and safety, and the gentle easily control of reaction conditions, the preparation process of dimethylaminobenzoic acid ester compound does not need to purify to intermediate, can successive reaction.Dangerous little in operating process, operate fairly simple, after reaction terminates, reaction solution obtains qualified product through distillation, rectifying or recrystallization.The method is environmental friendliness not only, and can reduce production cost.
Specific embodiment
In order to be illustrated more clearly in the present invention, nonlimiting examples is hereinafter taked to be described further.
Embodiment 1: to the preparation of dimethylamino Benzoyl chloride
In the four-hole bottle of 500ml, add N, accelerine (72.7g, 0.6mol) with 30ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 60ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 65 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, be down to room temperature, after first normal pressure, chlorobenzene is reclaimed in underpressure distillation, chlorobenzene has reclaimed, reclaim excess raw material N, accelerine, last rectification under vacuum obtains product 33.1g (collecting the condition of cut: 175 ~ 180 DEG C/15mmHg), yield 60%, purity 99.0%.
Embodiment 2: to the preparation of dimethylamino Benzoyl chloride
In the four-hole bottle of 500ml, add N, accelerine (121.2g, 1.0mol) with 60ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 120ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 65 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, be down to room temperature, after first normal pressure, chlorobenzene is reclaimed in underpressure distillation, chlorobenzene has reclaimed, reclaim excess raw material N, accelerine, last rectification under vacuum obtains product 44.1g (collecting the condition of cut: 175 ~ 180 DEG C/15mmHg), yield 80%, purity 99.1%.
Embodiment 3: the preparation of adjacent dimethylamino Benzoyl chloride
In the four-hole bottle of 500ml, add N, accelerine (121.2g, 1.0mol) with 60ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 120ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 40 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, adjacent dimethylamino Benzoyl chloride in gas-chromatography display reaction solution: be 75:25 to dimethylamino Benzoyl chloride, solvent and excess raw material are reclaimed, to purify adjacent dimethylamino Benzoyl chloride by rectification under vacuum.
Embodiment 4: the preparation of p-(dimethylamino)-benzoic acid methyl esters
In the four-hole bottle of 500ml, add N, accelerine (121.2g, 1.0mol) with 60ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 120ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 65 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, be down to temperature to 30 DEG C, slow dropping 12.8g anhydrous methanol, drip and finish, insulation reaction, TLC or GC monitors reaction, after reaction terminates, slowly reaction solution is put in 150ml water, stir hydrolysis, and control temperature is at about 25 DEG C, after 1h, stratification, organic phase saturated common salt water washing, with anhydrous sodium sulfate drying, vacuum distillation recovered solvent and excess raw material, carry out rectification under vacuum purification p-(dimethylamino)-benzoic acid methyl esters 43.0g (collecting the condition of cut: 101 ~ 105 DEG C/0.05mmHg) again, yield 80%, purity 99.2%.
Embodiment 5: the preparation of (dimethylamino)-ethyl benzoate
In the four-hole bottle of 500ml, add N, accelerine (121.2g, 1.0mol) with 60ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 120ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 65 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, be down to temperature to 30 DEG C, slow dropping 18.4g dehydrated alcohol, drip and finish, insulation reaction, TLC or GC monitors reaction, after reaction terminates, slowly reaction solution is put in 150ml water, stir hydrolysis, and control temperature is at about 25 DEG C, after 1h, stratification, organic phase saturated common salt water washing, with anhydrous sodium sulfate drying, vacuum distillation recovered solvent and excess raw material, carry out rectification under vacuum purification (dimethylamino)-ethyl benzoate 47.2g (collecting the condition of cut: 110 ~ 115 DEG C/0.02mmHg) again, yield 81%, purity 99.3%.
Embodiment 6: the preparation of IADB
In the four-hole bottle of 500ml, add N, accelerine (121.2g, 1.0mol) with 60ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 120ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 60 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, be down to temperature to 30 DEG C, slow dropping 35.3g primary isoamyl alcohol, drip and finish, insulation reaction, TLC or GC monitors reaction, after reaction terminates, slowly reaction solution is put in 150ml water, stir hydrolysis, and control temperature is at about 25 DEG C, after 1h, stratification, organic phase saturated common salt water washing, with anhydrous sodium sulfate drying, vacuum distillation recovered solvent and excess raw material, carry out rectification under vacuum purification IADB 55.8g (collecting the condition of cut: 150 ~ 155 DEG C/2.5mmHg) again, yield 79%, purity 99.5%.
Embodiment 7: the preparation of EHA
In the four-hole bottle of 500ml, add N, accelerine (121.2g, 1.0mol) with 60ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 120ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 60 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, be down to temperature to 30 DEG C, slow dropping 35.3g primary isoamyl alcohol, drip and finish, insulation reaction, TLC or GC monitors reaction, after reaction terminates, slowly reaction solution is put in 150ml water, stir hydrolysis, and control temperature is at about 25 DEG C, after 1h, stratification, organic phase saturated common salt water washing, with anhydrous sodium sulfate drying, vacuum distillation recovered solvent and excess raw material, carry out rectification under vacuum purification IADB 62.4g (collecting the condition of cut: 200 ~ 205 DEG C/3mmHg) again, yield 75%, purity 99.8%.
Embodiment 8: the preparation of adjacent dimethyl ethyl aminobenzoate
In the four-hole bottle of 500ml, add N, accelerine (121.2g, 1.0mol) with 60ml chlorobenzene, stir, by two (trichloromethyl) carbonic ether (29.7g, 0.1mol) be dissolved in 120ml chlorobenzene, slowly be added drop-wise to N, in the chlorobenzene solution of accelerine, 2h drips complete, then 40 DEG C are slowly warming up to, insulation reaction, TLC or GC monitors reaction, after reacting completely, be down to temperature to 30 DEG C, slow dropping 18.4g dehydrated alcohol, drip and finish, insulation reaction, TLC or GC monitors reaction, after reaction terminates, slowly reaction solution is put in 150ml water, stir hydrolysis, and control temperature is at about 25 DEG C, after 1h, stratification, organic phase saturated common salt water washing, with anhydrous sodium sulfate drying, adjacent dimethyl ethyl aminobenzoate in gas-chromatography display organic phase: (dimethylamino)-ethyl benzoate is 77:23, vacuum distillation recovered solvent and excess raw material, carry out rectification under vacuum again to purify adjacent dimethylaminobenzoic acid different ethyl ester ester 34.9g (collecting the condition of cut: 125 ~ 130 DEG C/3mmHg), yield 60%, purity 98.8%.
Claims (8)
1. the preparation method of a dimethylaminobenzoic acid ester compound (formula I):
Wherein, R represents the alkyl of 1-8 carbon atom;
1) by DMA, under presence or absence organic solvent, with two (trichloromethyl) carbonate reaction; With
2) react with alcohol subsequently;
The method need not isolation of intermediate products dimethylamino Benzoyl chloride.
2. the preparation method of a dimethylamino Benzoyl chloride (formula III):
By DMA, under presence or absence organic solvent, prepare with two (trichloromethyl) carbonate reaction.
3. the preparation method of dimethylaminobenzoic acid ester compound according to claim 1, is characterized in that the concrete steps comprised:
1), by DMA be dissolved in solvent, slowly drip two (trichloromethyl) carbonic ether wherein, drip and finish, slowly heat up, rise to certain temperature, insulation reaction;
2), react completely after, drip alcohol, drip finish, insulation reaction;
3), reaction terminate after, under stirring, reaction solution is slowly added drop-wise in water, then stratification, organic phase saturated common salt water washing;
4), the solution after washing is carried out vacuum distillation recovered solvent, excessive raw material, rectification under vacuum or recrystallization refined product.
4. the preparation method of dimethylamino Benzoyl chloride according to claim 2, is characterized in that the concrete steps comprised:
1), by DMA be dissolved in solvent, slowly drip two (trichloromethyl) carbonic ether wherein, drip and finish, slowly heat up, rise to certain temperature, insulation reaction;
2), reaction terminate after, reaction solution carries out vacuum distillation recovered solvent, excessive raw material, rectification under vacuum or recrystallization refined product.
5. the preparation method according to claim 3 and 4, is characterized in that the ratio of DMA described in step 1) and two (trichloromethyl) carbonic ether amount of substance is selected from 4-15:1.
6. the preparation method according to claim 3 and 4, is characterized in that solvent described in step 1) is selected from chlorobenzene, toluene, ethylene dichloride, benzene, methylene dichloride.
7. the preparation method according to claim 3 and 4, is characterized in that step 1) degree of intensification is selected from 40-80 DEG C.
8. preparation method according to claim 3, is characterized in that step 2) described in temperature of reaction be selected from-20-60 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410426414.0A CN105367436B (en) | 2014-08-27 | 2014-08-27 | A kind of preparation method of N, N- mesitylenic acid ester type compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410426414.0A CN105367436B (en) | 2014-08-27 | 2014-08-27 | A kind of preparation method of N, N- mesitylenic acid ester type compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105367436A true CN105367436A (en) | 2016-03-02 |
| CN105367436B CN105367436B (en) | 2018-04-24 |
Family
ID=55370131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410426414.0A Active CN105367436B (en) | 2014-08-27 | 2014-08-27 | A kind of preparation method of N, N- mesitylenic acid ester type compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105367436B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112707830A (en) * | 2020-12-28 | 2021-04-27 | 天津久日新材料股份有限公司 | Method for preparing tetraethyl mikrolon |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2882472A (en) * | 1955-11-02 | 1959-04-14 | Sprague Electric Co | Electrical capacitors |
-
2014
- 2014-08-27 CN CN201410426414.0A patent/CN105367436B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2882472A (en) * | 1955-11-02 | 1959-04-14 | Sprague Electric Co | Electrical capacitors |
Non-Patent Citations (2)
| Title |
|---|
| 季宝等: ""三光气的反应机理和应用"", 《科技情报开发与经济》 * |
| 缪裘缇等: ""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"", 《华东化工学院学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112707830A (en) * | 2020-12-28 | 2021-04-27 | 天津久日新材料股份有限公司 | Method for preparing tetraethyl mikrolon |
| CN112707830B (en) * | 2020-12-28 | 2023-09-29 | 天津久日新材料股份有限公司 | Preparation method of tetraethyl ketone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105367436B (en) | 2018-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104478797A (en) | Preparation method of nicotinamide fungicide namely boscalid | |
| CN105344341B (en) | Preparation method of solid catalyst for synthesizing dimethyl carbonate | |
| Kabalka et al. | A facile synthesis of aryl iodides via potassium aryltrifluoroborates | |
| CN105330600A (en) | Preparation method for Regorafenib hydrate | |
| CN104230839A (en) | Method for synthesizing N-substitued benzo-isothiazolone derivative | |
| CN109721548A (en) | A kind of preparation method of Fluoxastrobin | |
| CN102229529B (en) | Preparation method of (methyl) crylic acid phenylethanol ester compounds | |
| CN102850325A (en) | Preparation method of Dabigatran etexilate key intermediate | |
| CN105367436A (en) | Preparation method of N,N-dimethyl benzoate composite | |
| CN105198927B (en) | A kind of preparation method of benzoyl diphenyl phosphinoxides derivative | |
| CN107556262B (en) | A kind of preparation method of 2-substituted aryloxazole | |
| CN113416150A (en) | Novel synthesis method of lobaplatin intermediate | |
| CN101863782B (en) | Method for synthesizing ultraviolet photoinitiator of p-dimethylamin benzoic ether compounds | |
| CN101863954A (en) | Preparation method of N-tert-butyl-4-aza-5 alpha-androstane-3-ketone-17 beta-formamide | |
| CN103772225B (en) | A kind of preparation method of ultraviolet photoinitiator of p-dimethylamin benzoic ether compounds | |
| CN106699594A (en) | Preparation method of iopromide | |
| CN102786405B (en) | Preparation method for 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-acetone | |
| CN102775311B (en) | Preparation method of isooctyl salicylate | |
| CN103086898B (en) | Preparation method of diphenylamine or ring-substituted derivative thereof | |
| CN105503625A (en) | Method for synthesizing diethanolamine acrylate compounds | |
| CN103724213B (en) | A kind of synthetic method of 2,6-di-isopropyl-4-phenoxybenzamine | |
| CN103214423B (en) | A kind of preparation method of acrylic ester compound | |
| CN105237340A (en) | Novel synthesis method for 4,4,4-trifluorobutanol | |
| CN105272957B (en) | A kind of green synthesis method of neutral ion liquid catalyst glycerine converting carbonic ester | |
| CN108084077B (en) | A kind of synthetic method of zafirlukast intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |