CN103508880B - Method for synthesizing 3,5-dichlorobenzoyl chloride - Google Patents
Method for synthesizing 3,5-dichlorobenzoyl chloride Download PDFInfo
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- CN103508880B CN103508880B CN201310464758.6A CN201310464758A CN103508880B CN 103508880 B CN103508880 B CN 103508880B CN 201310464758 A CN201310464758 A CN 201310464758A CN 103508880 B CN103508880 B CN 103508880B
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- chloride
- triphosgene
- chloroformyl
- chlorination
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- GGHLXLVPNZMBQR-UHFFFAOYSA-N 3,5-dichlorobenzoyl chloride Chemical compound ClC(=O)C1=CC(Cl)=CC(Cl)=C1 GGHLXLVPNZMBQR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 30
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 16
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 29
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000010189 synthetic method Methods 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- -1 tertiary amine compounds Chemical class 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- YBONBWJSFMTXLE-UHFFFAOYSA-N 2,3-dichlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC(Cl)=C1Cl YBONBWJSFMTXLE-UHFFFAOYSA-N 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000007670 refining Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000012320 chlorinating reagent Substances 0.000 abstract 1
- NNTJKSMVNWGFTB-UHFFFAOYSA-N disulfuryl chloride Chemical compound ClS(=O)(=O)OS(Cl)(=O)=O NNTJKSMVNWGFTB-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 20
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 6
- WHIHIKVIWVIIER-UHFFFAOYSA-N 3-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC(Cl)=C1 WHIHIKVIWVIIER-UHFFFAOYSA-N 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 4
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 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
- 239000000383 hazardous chemical Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012970 tertiary amine catalyst Substances 0.000 description 3
- CXKCZFDUOYMOOP-UHFFFAOYSA-N 3,5-dichlorobenzoic acid Chemical class OC(=O)C1=CC(Cl)=CC(Cl)=C1 CXKCZFDUOYMOOP-UHFFFAOYSA-N 0.000 description 2
- FCOHEOSCARXMMS-UHFFFAOYSA-N Oxaziclomefone Chemical compound C1OC(C)=C(C=2C=CC=CC=2)C(=O)N1C(C)(C)C1=CC(Cl)=CC(Cl)=C1 FCOHEOSCARXMMS-UHFFFAOYSA-N 0.000 description 2
- IBZHOAONZVJLOB-UHFFFAOYSA-N Tridiphane Chemical compound ClC1=CC(Cl)=CC(C2(CC(Cl)(Cl)Cl)OC2)=C1 IBZHOAONZVJLOB-UHFFFAOYSA-N 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006324 decarbonylation Effects 0.000 description 2
- 238000006606 decarbonylation reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- DPCQFBWPRXQASW-UHFFFAOYSA-N 1,3-dichloro-5-ethylbenzene Chemical compound CCC1=CC(Cl)=CC(Cl)=C1 DPCQFBWPRXQASW-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000005602 Propyzamide Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QWENMOXLTHDKDL-UHFFFAOYSA-M pentoxymethanedithioate Chemical compound CCCCCOC([S-])=S QWENMOXLTHDKDL-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- PHNUZKMIPFFYSO-UHFFFAOYSA-N propyzamide Chemical compound C#CC(C)(C)NC(=O)C1=CC(Cl)=CC(Cl)=C1 PHNUZKMIPFFYSO-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing 3,5-dichlorobenzoyl chloride. The method comprises the following steps: carrying out sulfonation on benzoyl chloride by sulfur trioxide to obtain 5-chloroformyl metaphenylene disulfonic acid; carrying out chlorination by catalyzed triphosgene to obtain 5-chloroformyl metaphenylene disulfuryl chloride; finally, carrying out removal of sulfur dioxide chlorination to obtain 3,5-dichlorobenzoyl chloride. Compared with an existing preparation method, the method disclosed by the invention has the characteristics of stable chlorinating agent, high production safety, small amount of three wastes, no requirement for recovering and treating a great amount of dangerous byproducts, no requirement for refining a coarse product, low production cost and the like and is suitable for industrial production.
Description
Technical field
The invention belongs to field of fine chemical, particularly the synthetic method of agrochemicals intermediate 3,5-dichlorobenzoyl chloride.
Background technology
3,5-dichlorobenzoyl chloride is widely used fine-chemical intermediate, particularly the synthetic herbicide pentyl xanthate (important intermediate of propyzamide), oxaziclomefone (oxaziclomefone) and tridiphane (tridiphane) etc.
The document synthetic route of 3, the 5-dichlorobenzoyl chlorides reported mainly contains following several:
1. US Patent No. 3931300, chemical engineer (2009, (6), 68-70), chemical industry progress (2002, 21(10), 756-757), German patent DE 2721133, anthranilic acid such as report such as German patent DE 2659147 grade, para-amino benzoic acid or both mixtures obtain 3 through chlorizating agent chlorination, 5-bis-chloro-o-amino benzoic acid, 3, 5-dichloro para-amino benzoic acid or both mixtures, then 3 are obtained through diazotization Reductive elimination amino, 5-dichlorobenzoic acid, finally by chlorizating agent chlorination obtained 3, 5-dichlorobenzoyl chloride, as follows for the synthetic route of anthranilic acid:
The method step is many, and total recovery is low, and cost of material is high, pollutes large, poor stability.
2. Journal of American Chemical Society (1951,73,455-456) reports that 3,5-toluene dichloride is through obtained 3, the 5-dichloro benzenyl trichloride of chlorination, then through obtained 3, the 5-dichlorobenzoyl chloride of controlled hydrolysis; US Patent No. 2999879 reports that 3,5-dichloro ethylbenzene is through being oxidized obtained 3,5-dichlorobenzoic acids, then obtains 3,5-dichlorobenzoyl chloride through chlorination.3,5-toluene dichloride also can be oxidized to 3,5-dichlorobenzoic acid, then through obtained 3, the 5-dichlorobenzoyl chloride of chlorination.Synthetic route is as follows:
This route raw material is not easy to obtain, and lacks industrial value.
3. US Patent No. 3869510, Japanese Patent JP 57193434 etc. report that m-phthaloyl chloride obtains 5-chlorine m-phthaloyl chloride through catalytic chlorination, then at PdCl
2, Pd/BaSO
4, Pd/Al
2o
3carry out selectivity decarbonylation base and obtain 3,5-dichlorobenzoyl chlorides Deng being heated to more than 245 DEG C under existence, synthetic route is as follows:
This route cost of material is high, and decarbonylation catalyst is expensive, and reaction conditions requires higher.
4. Japanese Patent JP 7089899 reports that m-chlorobenzoyl chloride is through obtained 3, the 5-dichlorobenzoyl chloride of high temperature gas phase chlorination one step, and synthetic route is as follows:
This route raw material sources difficulty, price is high, and chlorization condition is comparatively harsh.
5. US Patent No. 3689546 to report between 5-chloroformyl benzene-disulfo-chloride at relatively high temperatures logical chlorine slough sulfurous gas chlorination simultaneously and obtain 3,5-dichlorobenzoyl chloride, yield is up to 94%, mention that between raw material 5-chloroformyl, benzene-disulfo-chloride can be synthesized by currently known methods simultaneously, as through sulphur trioxide or oleum sulfonation, then obtain through the chlorination of chlorizating agent as phosphorus pentachloride or Phosphorus Oxychloride.Synthetic route is as follows:
It is few that this route has reactions steps, and raw material is cheap and easy to get, sulphonation recovery advantages of higher, but phosphorus pentachloride is monitored hazardous chemical, molecular weight is large and unit consumption is high, simultaneously the monitored hazardous chemical phosphorus oxychloride of by-product equimolar amount, needs to recycle or process.In addition, density and the boiling point of by-product phosphorus oxychloride are higher, are difficult to thoroughly from product, be separated removing, cause the yield of the 3rd step removal sulfur dioxide chlorination reaction and product content to decline.
Sum up above synthetic route, be still best with synthetic route 5, it is also one of current industrialized method.But still there is shortcoming as above namely in this synthetic method: during the chlorination of second step phosphorus pentachloride, the phosphorus oxychloride (often consuming the phosphorus oxychloride that 1 ton of phosphorus pentachloride produces 0.74 ton) of by-product equimolar amount, need to recycle or process, phosphorus pentachloride and phosphorus oxychloride are monitored hazardous chemical.In addition, by-product phosphorus oxychloride boiling point is higher, is difficult to thoroughly from product, be separated removing, affect the removal sulfur dioxide chlorination reaction of the 3rd step, cause the yield of product 3,5-dichlorobenzoyl chloride to decline, content is on the low side, needs the content that just can reach more than 98% through recrystallization.In addition, also there are the three wastes and the problem such as equipment corrosion is serious, production security is poor in this technique, so the technique improving existing 3,5-dichlorobenzoyl chlorides has important industrial value.
Summary of the invention
In order to the shortcoming such as overcome the three wastes and seriously corroded in existing 3,5-dichlorobenzoyl chloride technologies of preparing, harmful influence treatment capacity is large, production security is low, cost is high, product content is low, the invention provides a kind of synthetic method of 3,5-dichlorobenzoyl chlorides.
The synthetic method of one 3, the 5-dichlorobenzoyl chloride that the present invention proposes, comprises the sulfonation reaction of the first step: take Benzoyl chloride as raw material, benzene disulfonic acid through between SO 3 sulfonated obtained 5-chloroformyl; The catalytic chlorination reaction of second step: take triphosgene as chlorizating agent, take tertiary amine compounds as catalyzer, catalyzer usage quantity is 0.2% to 5.0% of triphosgene weight, temperature of reaction is 100-120 DEG C, between 5-chloroformyl, benzene disulfonic acid and triphosgene are reacted in inert solvent, obtain benzene-disulfo-chloride between 5-chloroformyl; The removal sulfur dioxide chlorination reaction of the 3rd step: under chlorine being passed into the reaction solution liquid level of second step, between 5-chloroformyl, benzene-disulfo-chloride is through obtained 3, the 5-dichlorobenzoyl chloride of removal sulfur dioxide chlorination.
In the chlorination reaction of the present invention's benzene disulfonic acid between 5-chloroformyl, phosphorus pentachloride is substituted as chlorizating agent using triphosgene, and add tertiary amine catalyst, catalysis triphosgene chlorination two sulfonic groups become chlorosulfonyl, by product carbonic acid gas and the hydrogenchloride of reaction are gas, not only be easy to remove completely from reaction system, can also promote that reaction mixture is even, make chlorination more complete, overcome by-product in prior art and not easily recycle harmful influence phosphorus oxychloride in a large number, affect next step removal sulfur dioxide chlorination reaction cause product yield and content on the low side, thick product just need can reach the deficiencies such as the content of more than 98% through recrystallization.
Synthetic route of the present invention is as follows:
Described tertiary amine catalyst consumption is the 0.2%-5.0% of triphosgene weight, can both realize object of the present invention, the 0.5%-2.0% of preferred scheme to be tertiary amine catalyst consumption be triphosgene weight.
Preferred tertiary amines catalyst is tri-n-butylamine, N-methylmorpholine, 1,4-lupetazin, N, accelerine, N, N-Diethyl Aniline, N, N, N ', N '-Tetramethyl Ethylene Diamine (TMEDA), triethylenediamine (DABCO), 1,8-diazabicyclo [5.4.0] hendecene-7(DBU), 1,5-diazabicyclo [4.3.0] nonene-5(DBN) and one or both of DMAP (DMAP).
Described inert solvent refer to not with any material that the present invention relates in reaction process, comprise raw material, intermediate, product and by product and react, also can not decompose at reaction conditions, the solvent of oxidation etc.It is an option that the solvent that such class character such as such as o-Xylol, m-xylene, p-Xylol, ethylbenzene, isopropyl benzene, chlorobenzene, Mixed XYLENE are close, what can reach best effect is preferred Mixed XYLENE and chlorobenzene.
The preferred 100-120 DEG C of described second step temperature of reaction, preferred reaction time 1-10h.
The present invention take Benzoyl chloride as raw material; through SO 3 sulfonated, the chlorination of catalysis triphosgene, removal sulfur dioxide chlorination three-step reaction obtained 3; 5-dichlorobenzoyl chloride; synthesis technique is simple, reaction conditions is gentle, raw material is easy to get, product yield is high, and avoid and reclaim or process a large amount of harmful influence, production security is high; and containing 3 in crude product; 5-dichlorobenzoyl chloride is not less than 98%, directly can use as intermediate, therefore have very large industrial value without the need to refining.
Embodiment
Following examples are raw materials used is technical grade, without being further purified.Product content measures with gas-chromatography normalization method.
embodiment 1140.5g (1.0mol) Benzoyl chloride is heated to 130 DEG C, and drip 176g (2.2mol) sulphur trioxide, control 2h drips off.In dropping process, temperature is increased to 170 DEG C gradually, drips off and continue be warming up to 220 DEG C and keep 16h.Be cooled to 120 DEG C, add catalyzer DMAP (DMAP) 2.0g and Mixed XYLENE 60g.Be divided into 6 batches in 1h and add triphosgene 218g(2.2mol), insulation reaction 3h.Vacuum distillation recovered solvent, to interior temperature 150 DEG C end.Chlorine is passed into reaction solution liquid level with the speed of 0.4g/min at 175 DEG C of temperature under, sulfur dioxide gas is had to overflow immediately.No longer include sulfurous gas after reaction 2.5h to release.Be cooled to 50 DEG C, underpressure distillation, obtain crude product 182g, yield 86.8%, wherein containing 3,5-dichlorobenzoyl chloride 98.6%, m-chlorobenzoyl chloride 0.7%, 1,3,5-trichlorobenzene 0.2%.
embodiment 2140.5g (1.0mol) Benzoyl chloride is heated to 140 DEG C, and drip 176g (2.2mol) sulphur trioxide, control 2h drips off.In dropping process, temperature is increased to 170 DEG C gradually, drips off and continue be warming up to 220 DEG C and keep 16h.Be cooled to 100 DEG C, add catalyzer triethylenediamine (DABCO) 1.1g and chlorobenzene 50g.Be divided into 6 batches in 1h and add triphosgene 218g(2.2mol), insulation reaction 4h.Vacuum distillation recovered solvent, to interior temperature 150 DEG C end.Under chlorine being passed into reaction solution liquid level with the speed of 0.4g/min under heat-retaining condition, sulfur dioxide gas is had to overflow immediately.No longer include sulfurous gas after reaction 2.0h to release.Be cooled to 50 DEG C, underpressure distillation, obtain crude product 179g, yield 85.4%, containing 3,5-dichlorobenzoyl chloride 98.3%, m-chlorobenzoyl chloride 1.0%, 1,3,5-trichlorobenzene 0.3%.
comparative example 1140.5g (1.0mol) Benzoyl chloride is heated to 125 DEG C, and drip 176g (2.2mol) sulphur trioxide, control 2h drips off.In dropping process, temperature is increased to 170 DEG C gradually, drips off and continue be warming up to 220 DEG C and keep 16h.Be cooled to 120 DEG C, add 307g(2.0mol) POCl
3, keep 120 DEG C to react 2h, then add 229g(1.1mol) and PCl
5, 120 DEG C are continued reaction 2h.Change backflow into distillation, normal pressure steams phosphorus oxychloride, to interior temperature 180 DEG C end.System temperature is risen to 220 DEG C, under chlorine being passed into reaction solution liquid level with the speed of 0.25g/min, have sulfur dioxide gas to overflow immediately.After reacting about 5h, no longer include sulfurous gas and release.Be cooled to 50 DEG C, underpressure distillation, obtain crude product 164g, yield 78.2%, containing 3,5-dichlorobenzoyl chloride 91.4%, m-chlorobenzoyl chloride 3.2%, 1,3,5-trichlorobenzene 2.5%.
comparative example 2140.5g (1.0mol) Benzoyl chloride is heated to 125 DEG C, and drip 176g (2.2mol) sulphur trioxide, control 2h drips off.In dropping process, temperature is increased to 170 DEG C gradually, drips off and continue be warming up to 220 DEG C and keep 16h.Be cooled to 120 DEG C, add 307g(2.0mol) POCl
3, keep 120 DEG C to react 2h, then add 229g(1.1mol) and PCl
5, 120 DEG C are continued reaction 2h.Change backflow into distillation, normal pressure steams phosphorus oxychloride, to interior temperature 180 DEG C end.System temperature is risen to 220 DEG C, under chlorine being passed into reaction solution liquid level with the speed of 0.25g/min, have sulfur dioxide gas to overflow immediately.After reacting about 5h, no longer include sulfurous gas and release.Be cooled to 50 DEG C, underpressure distillation, obtain crude product 161.3g, yield 76.9%, containing 3,5-dichlorobenzoyl chloride 92.0%, m-chlorobenzoyl chloride 2.9%, 1,3,5-trichlorobenzene 2.7%.
The technician of the industry should understand; the present invention is not restricted to the described embodiments; describe in above-described embodiment and specification sheets just in order to principle of the present invention is described; without departing from the spirit and scope of the present invention; the present invention also has the changes and improvements of various unsubstantiality, and these all fall in the scope of protection of present invention.
Claims (5)
1. the synthetic method of a dichlorobenzoyl chloride, comprises the sulfonation reaction of the first step: take Benzoyl chloride as raw material, benzene disulfonic acid through between SO 3 sulfonated obtained 5-chloroformyl; The catalytic chlorination reaction of second step: take triphosgene as chlorizating agent, take tertiary amine compounds as catalyzer, catalyzer usage quantity is 0.2% to 5.0% of triphosgene weight, temperature of reaction is 100-120 DEG C, between 5-chloroformyl, benzene disulfonic acid and triphosgene are reacted in inert solvent, obtain benzene-disulfo-chloride between 5-chloroformyl; The removal sulfur dioxide chlorination reaction of the 3rd step: under chlorine being passed into the reaction solution liquid level of second step, between 5-chloroformyl, benzene-disulfo-chloride obtains 3,5-dichlorobenzoyl chloride through removal sulfur dioxide chlorination; Described inert solvent is o-Xylol, m-xylene, p-Xylol, ethylbenzene, isopropyl benzene, chlorobenzene, Mixed XYLENE, and its consumption is the 20-40% of triphosgene weight.
2. the synthetic method of 3,5-dichlorobenzoyl chlorides as claimed in claim 1, is characterized in that: the usage quantity of tertiary amine compounds is 0.5% to 2.0% of triphosgene weight.
3. as claimed in claim 13, the synthetic method of 5-dichlorobenzoyl chloride, it is characterized in that: described tertiary amine compounds is tri-n-butylamine, N-methylmorpholine, Isosorbide-5-Nitrae-lupetazin, DMA, N, N-Diethyl Aniline, N, N, N ', N '-Tetramethyl Ethylene Diamine, triethylenediamine, 1, one or both of 8-diazabicyclo [5.4.0] hendecene-7,1,5-diazabicyclo [4.3.0] nonene-5 and DMAP.
4. as claimed in claim 13,5-dichlorobenzoyl chloride synthetic method, it is characterized in that the sulfonation reaction of the first step: 1.0mol Benzoyl chloride is heated to 130 DEG C, drip 2.2mol sulphur trioxide, control 2h drips off, in dropping process, temperature is increased to 170 DEG C gradually, drips off and continue be warming up to 220 DEG C and keep 16h; The catalytic chlorination reaction of second step: aforementioned reactants is cooled to 120 DEG C, adds catalyzer DMAP 2.0g and Mixed XYLENE 60g, then add triphosgene 2.2mol, insulation reaction 3h, vacuum distillation recovered solvent in batches, to interior temperature 150 DEG C end; The removal sulfur dioxide chlorination reaction of the 3rd step: chlorine is passed into reaction solution liquid level with the speed of 0.4g/min at 175 DEG C of temperature under, releasing to no longer including sulfurous gas after reaction 2.5h, being then cooled to 50 DEG C, underpressure distillation, obtaining crude product.
5. as claimed in claim 13,5-dichlorobenzoyl chloride synthetic method, it is characterized in that the sulfonation reaction of the first step: 1.0mol Benzoyl chloride is heated to 140 DEG C, drip 2.2mol sulphur trioxide, control 2h drips off, in dropping process, temperature is increased to 170 DEG C gradually, drips off and continue be warming up to 220 DEG C and keep 16h; The catalytic chlorination reaction of second step: aforementioned reactants is cooled to 100 DEG C, adds catalyzer triethylenediamine 1.1g and chlorobenzene 50g, then add triphosgene 2.2mol, insulation reaction 4h, vacuum distillation recovered solvent in batches, to interior temperature 150 DEG C end; The removal sulfur dioxide chlorination reaction of the 3rd step: under chlorine being passed into reaction solution liquid level with the speed of 0.4g/min under heat-retaining condition, no longer includes sulfurous gas after reaction 2.0h and releases, be then cooled to 50 DEG C, underpressure distillation, obtain crude product.
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| CN105111066B (en) * | 2015-08-06 | 2016-10-19 | 连云港市三联化工有限公司 | 3,5 dichlorobenzoyl chloride synthetic methods |
| CN105837432A (en) * | 2016-05-03 | 2016-08-10 | 山东润博生物科技有限公司 | Novel preparation method of 3,5-dichlorobenzoyl chloride |
| CN105906502A (en) * | 2016-05-03 | 2016-08-31 | 山东润博生物科技有限公司 | Preparation method of 3,5-dichlorobenzoyl chloride |
| CN106349121B (en) * | 2016-08-16 | 2018-08-17 | 上海绿麟达新材料科技有限公司 | The preparation method of one kind 3,5- dichlorobenzoyl chlorides |
| CN107879930A (en) * | 2017-05-10 | 2018-04-06 | 湖南比德生化科技股份有限公司 | A kind of method that 3,5 dichlorobenzoyl chlorides are prepared with chlorobenzoyl chloride |
| CN107805198A (en) * | 2017-11-02 | 2018-03-16 | 南京工业大学连云港工业技术研究院 | The synthetic method of 3,5 dichlorobenzoyl chlorides |
| CN111718286A (en) * | 2020-07-23 | 2020-09-29 | 邓博天 | Industrial production method of aromatic hydrocarbon sulfonyl chloride with power supply group |
| CN112299988A (en) * | 2020-11-12 | 2021-02-02 | 盐城丰诺化工有限公司 | Formula and preparation method of pesticide intermediate 3, 5-dichlorobenzoyl chloride |
| CN112961162B (en) * | 2021-03-30 | 2022-09-30 | 泉州师范学院 | Organic-inorganic hybrid manganese halide luminescent material and preparation method thereof |
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