CN116239465B - Preparation method of 4,4' -diphenyl ether diformyl chloride - Google Patents
Preparation method of 4,4' -diphenyl ether diformyl chloride Download PDFInfo
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- CN116239465B CN116239465B CN202310068931.4A CN202310068931A CN116239465B CN 116239465 B CN116239465 B CN 116239465B CN 202310068931 A CN202310068931 A CN 202310068931A CN 116239465 B CN116239465 B CN 116239465B
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- dicarboxylic acid
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- -1 diformyl chloride Chemical compound 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000008213 purified water Substances 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 claims description 7
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 125000005117 dialkylcarbamoyl group Chemical group 0.000 claims description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 claims description 3
- OFCCYDUUBNUJIB-UHFFFAOYSA-N n,n-diethylcarbamoyl chloride Chemical compound CCN(CC)C(Cl)=O OFCCYDUUBNUJIB-UHFFFAOYSA-N 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
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 238000004128 high performance liquid chromatography Methods 0.000 description 13
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000001514 detection method Methods 0.000 description 5
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002577 polybenzoxazole Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YAWIAFUBXXPJMQ-UHFFFAOYSA-N 1-bromo-4-(4-bromophenoxy)benzene Chemical compound C1=CC(Br)=CC=C1OC1=CC=C(Br)C=C1 YAWIAFUBXXPJMQ-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- SAUMVKNLVQDHMJ-UHFFFAOYSA-N dichlorine trioxide Inorganic materials ClOCl(=O)=O SAUMVKNLVQDHMJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- 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
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/06—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid amides
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 4,4' -diphenyl ether diformyl chloride, which comprises the following steps: the method is characterized in that diphenyl ether is used as a raw material, 4' -diphenyl ether dimethylformamide is synthesized by utilizing Friedel-crafts acylation reaction, and then a final product is obtained through two steps of hydrolysis and acyl chlorination. Compared with the prior method, the method has the advantages of lower cost and energy consumption, higher yield, molar yield up to 90 percent, safer operation, simple operation, and easy industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of 4,4' -diphenyl ether diformyl chloride.
Background
4,4' -Diphenylether dicarboxylic acid chloride, white solid, molecular formula: c 14H8Cl2O3, relative molecular weight: 295.1175, cas No.: 7158-32-9, the structural formula is as follows:
Polybenzoxazole (PBO) has excellent moisture resistance, oxidation resistance, ultraviolet resistance, radiation resistance and other properties, and still maintains good comprehensive properties at a high temperature of 500 ℃, so that it is widely applied to aerospace materials. 4,4' -diphenylether dicarboxylic acid dichloride is an important monomer for synthesizing PBO, so how to develop an efficient and high-quality synthesis process thereof is widely paid attention to by workers in the field. The synthesis method of 4,4' -diphenyl ether dicarboxylic acid mainly comprises the steps of high-temperature condensation and hydrolysis of p-nitroaniline (CN 1052300A); friedel-crafts acetylation of diphenyl ether followed by oxidation to acid (EP 1211235A 2); 4,4' -dibromodiphenyl ether noble metal catalyzed carbointercalation (Russian Journal of APPLIED CHEMISTRY 2005,78,1844); and oxidizing methyl into acid (CN 1004808B) after condensing p-halotoluene and p-methylphenol at high temperature. However, the above prior art requires severe reaction conditions such as high temperature, high pressure or oxidation, and the like, and has high cost and low yield.
Disclosure of Invention
The invention aims to provide a preparation method of 4,4' -diphenyl ether diformyl chloride, which solves the problems of high temperature, high pressure or oxidation and other harsh reaction conditions, high cost and lower yield in the prior art.
In order to achieve the above object, the present invention provides a method for preparing 4,4' -diphenylether dicarboxylic acid dichloride, comprising the steps of:
s1, diphenyl ether and carbamoyl chloride or dialkyl carbamoyl chloride are catalyzed by Lewis acid to obtain an intermediate I;
s2, hydrolyzing the intermediate I under the action of a hydrolysis reagent to obtain an intermediate II;
S3, performing an acyl chlorination reaction on the intermediate II under the action of an acyl chlorination reagent to obtain the 4,4' -diphenyl ether diformyl chloride.
Preferably, the molar ratio of diphenyl ether to carbamoyl chloride is 1:2 to 1:5; the molar ratio of the diphenyl ether to the dialkyl carbamoyl chloride is 1:2-1:5; the molar ratio of the Lewis acid to the diphenyl ether is 2:1-3:1, and the reaction temperature is 20-120 ℃.
Preferably, the dialkylcarbamoyl chloride comprises dimethylcarbamoyl chloride and diethylcarbamoyl chloride.
Preferably, the lewis acid is one of aluminum chloride, ferric chloride, zinc chloride, manganese chloride and boron trifluoride.
Preferably, the solvent used in step S1 is one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, chlorobenzene or dichlorobenzene.
Preferably, in the step S2, the hydrolysis reagent is one of lithium hydroxide, sodium hydroxide or potassium hydroxide, the molar ratio of the intermediate I to the hydrolysis reagent is 1:3-1:20, and the reaction temperature is 20-80 ℃.
Preferably, the solvent used in step S2 is methanol, ethanol or a mixture of tetrahydrofuran and water.
Preferably, the acyl chloride reagent in the step S3 is one of thionyl chloride, oxalyl chloride or triphosgene; the mol ratio of the intermediate II to the acyl chloride reagent is 1:2-1:20, and the acyl chloride reaction temperature is 40-120 ℃.
Preferably, the solvent used in step S3 is one of toluene, tetrahydrofuran, DMF, dichloromethane, dichloroethane.
Preferably, the preparation method of the 4,4' -diphenyl ether diformyl chloride comprises the following steps:
S1, adding 1.0mol of diphenyl ether and 850mL of dichloroethane, stirring at 0-5 ℃ while adding 2.4mol of aluminum trichloride, and adding 2.2mol of carbamoyl chloride in portions within 1.5 hours; reacting for 16h at 50 ℃, and cooling to room temperature; 700mL of 12% diluted hydrochloric acid was added at 0deg.C; stirring at room temperature for 20min, standing for layering, washing the obtained organic phase with purified water twice, and distilling under reduced pressure to remove solvent to obtain light yellow oily substance; adding methanol for recrystallization to obtain 4,4' -diphenyl ether dimethylformamide; the batch adding method comprises the steps of controlling the temperature to be 0-5 ℃, stopping adding when the temperature is close to 5 ℃, stirring until the temperature is reduced, and continuing adding;
S2, taking 0.780mol of 4,4' -diphenyl ether dimethylformamide, 500g of methanol, 300g of water and 4.68mol of sodium hydroxide, and stirring at 60 ℃ for 8 hours; removing methanol by reduced pressure distillation; dropwise adding 36% concentrated hydrochloric acid into the water phase until the pH value is=2-3, and precipitating white solid; filtering, and vacuum drying at 80 ℃ for 12 hours to obtain 4,4' -diphenyl ether dicarboxylic acid;
S3, taking 0.697mol of 4,4' -diphenyl ether dicarboxylic acid, 300mL of dichloroethane, 2.09mol of thionyl chloride and 0.2mL of LDMF, heating to 83 ℃, refluxing and stirring for 3 hours; removing the solvent by reduced pressure distillation, adding toluene for recrystallization, and obtaining the 4,4' -diphenyl ether diformyl chloride.
Compared with the prior art, the invention has the beneficial effects that:
The invention takes diphenyl ether as raw material, synthesizes 4,4' -diphenyl ether dimethylamide by Friedel-crafts acylation reaction, and then obtains a final product through two steps of hydrolysis and acyl chlorination.
(1) The invention uses the low-cost diphenyl ether as the raw material, thereby greatly reducing the cost.
(2) The invention does not need high temperature, all reactions can be carried out below 100 ℃, and the energy consumption is reduced.
(3) The invention has no oxidation step, and greatly reduces the safety risk and waste emission caused by the oxidant.
(4) The invention realizes conversion through three steps of reactions, the molar yield can reach 90%, the operation is simple, and the industrial production is easy.
Drawings
FIG. 1 is an ESI-MS spectrum of 4,4' -diphenylether dimethylamide prepared in example 1;
FIG. 2 is an ESI-MS spectrum of 4,4' -diphenylether dicarboxylic acid obtained in example 1;
FIG. 3 is a chart showing the ESI-MS spectrum of 4,4' -diphenylether dicarboxylic acid dichloride prepared in example 1 dissolved in methanol;
FIG. 4 is an ESI-MS spectrum of 4,4'- (N, N' -dimethylformamide) diphenyl ether prepared in example 2;
FIG. 5 is an ESI-MS spectrum of 4,4'- (N, N' -diethylformamide) diphenyl ether prepared in example 3.
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited in any way.
Example 1:
step (1): into a 2L reaction flask were charged diphenyl ether (170.2 g,1.0 mol) and 850mL of dichloroethane, and aluminum trichloride (320.0 g,2.4 mol) was added with stirring at 0 to 5 ℃. Carbamoyl chloride (174.9 g,2.2 mol) was then added in portions at the same temperature over about 1.5 hours. The reaction is carried out for 16h at 50 ℃ until the raw materials disappear, the HPLC is controlled to be finished, and the temperature is reduced to the room temperature. The reaction solution was slowly poured into 700mL of 12% diluted hydrochloric acid at 0deg.C. Stirring at room temperature for 20min, standing for layering, washing the obtained organic phase with purified water twice, and distilling under reduced pressure to remove solvent to obtain light yellow oily substance. Adding methanol for recrystallization to obtain 241.8g of white solid intermediate (I), wherein the purity is 99.8 percent (HPLC), and the melting point is 145.2-146.5 ℃. Step (1) molar yield: 94.4%.
The method of batch addition is to observe the reaction temperature, the temperature cannot exceed 5 ℃, and the addition is stopped when the reaction temperature approaches, and the reaction is continued after the reaction temperature is stirred to be reduced.
The ESI-MS detection of the above products is carried out, and the result is shown in FIG. 1, and can be seen from FIG. 1: ESI-MS showed the product molecular weight to be 256.1.
Intermediate I is 4,4' -diphenylether dimethylformamide, namely:
Step (2): the intermediate (I) (200.0 g,0.780 mol) obtained in the above step was taken and put into a 2L three-necked flask, and methanol (500 g), purified water (300 g) and sodium hydroxide (187.3 g,4.68 mol) were added thereto and stirred at 60℃for 8 hours. Methanol was distilled off under reduced pressure. 36% concentrated hydrochloric acid was added dropwise to the aqueous phase until ph=2 to 3, and a white solid was precipitated. Filtering, leaching the filter cake by purified water, and vacuum drying at 80 ℃ for 12 hours to obtain 198.2g of white solid intermediate (II) with purity of 99.9% (HPLC) and melting point of 330.3-331.7 ℃. Step (2) molar yield: 98.3%.
ESI-MS detection of the above products can be seen in FIG. 2: ESI-MS showed 258.1 molecular weight of the product.
Intermediate II is 4,4' -diphenyl ether dicarboxylic acid, namely:
Step (3): intermediate (II) (180.0 g,0.697 mol), dichloroethane (300 mL), thionyl chloride (248.6 g,2.09 mol) and 0.2mL of LDMF obtained in the above steps were successively added to a 2L three-necked flask, and the mixture was heated to 83℃and stirred under reflux for 3 hours. After the medium control reaction is finished, the solvent is distilled off under reduced pressure, and the residue is added with toluene for recrystallization to obtain 199.2g of white crystal finished product with the purity of 99.7 percent (HPLC) and the melting point of 89.9-92.5 ℃. Step (3) molar yield: 97.0%. The total molar yield of the three steps is as follows: 90.0%.
ESI-MS detection was performed by dissolving the above product in methanol, and the results are shown in FIG. 3, and it can be seen that: ESI-MS showed a molecular weight of 286.1 for the methanol-derived product, demonstrating that the product was diacid chloride.
The product was 4,4' -diphenylether dicarboxylic acid chloride:
Example 2:
Step (1): into a 1L reaction flask were charged diphenyl ether (85.1 g,0.5 mol) and 400mL of dichloroethane, and aluminum trichloride (140.0 g,1.05 mol) was added with stirring at 0 to 5 ℃. Then, dimethylcarbamoyl chloride (112.9 g,1.05 mol) was added in portions at the same temperature for about 1 hour. Reacting for 16h at 50 ℃, finishing the HPLC central control reaction, cooling to room temperature. The reaction solution was slowly poured into 400mL of dilute hydrochloric acid at 0 ℃. Stirring at room temperature for 20min, standing for layering, washing the obtained organic phase with purified water twice, and distilling under reduced pressure to remove solvent to obtain light yellow oily substance. Methanol is added for recrystallization to obtain 139.8g of white solid intermediate (I), the purity is 99.2 percent (HPLC), and the melting point is 154.0-155.3 ℃. Step (1) molar yield: 89.5%.
ESI-MS detection of the above products can be seen in FIG. 4: ESI-MS showed a molecular weight of 312.2.
Step (2): the intermediate (I) (100 g,0.320 mol) obtained in the above step was taken and put into a 1L three-necked flask, and methanol (200 g), purified water (150 g) and sodium hydroxide (76.8 g,1.92 mol) were added thereto and stirred under reflux for 16 hours. Methanol was distilled off under reduced pressure. 36% concentrated hydrochloric acid was added dropwise to the aqueous phase until ph=2 to 3, and a white solid was precipitated. Filtering, leaching the filter cake by purified water, and vacuum drying at 80 ℃ for 12 hours to obtain 78.3g of white solid intermediate (II) with purity of 99.7% (HPLC) and melting point of 330.3-331.9 ℃. Step (2) molar yield: 94.7%.
Step (3): intermediate (II) (75 g,0.290 mol), dichloroethane (300 mL), thionyl chloride (103.7 g,0.871 mol) and 0.2mL of DMF obtained in the above step were sequentially added to a 2L three-necked flask, and the mixture was heated to 83℃and stirred under reflux for 3 hours. After the medium control reaction is finished, the solvent is distilled off under reduced pressure, and the residue is added with toluene for recrystallization to obtain 84.6g of white crystal finished product with the purity of 99.7 percent (HPLC) and the melting point of 89.9-92.4 ℃. Step (3) molar yield: 98.7%. The total molar yield of the three steps is as follows: 83.7%.
Example 3:
Step (1): into a 1L reaction flask were charged diphenyl ether (85.1 g,0.5 mol) and 400mL of dichloroethane, and aluminum trichloride (150.7 g,1.16 mol) was added with stirring at 0 to 5 ℃. Then, diethylcarbamoyl chloride (169.2 g,1.27 mol) was added in portions at the same temperature for about 1 hour. And (3) reacting for 16 hours at 50 ℃, finishing the central control reaction, and cooling to room temperature. The reaction solution was slowly poured into 400mL of dilute hydrochloric acid at 0 ℃. Stirring at room temperature for 20min, standing for layering, washing the obtained organic phase with purified water twice, and distilling under reduced pressure to remove solvent to obtain light yellow oily substance. Methanol was added to recrystallise to give 170.3g of intermediate (I) as a white solid, 99.2% pure (HPLC), melting point 156 ℃. Step (1) molar yield: 87.4%.
ESI-MS detection of the above products can be seen in FIG. 5: ESI-MS showed the product molecular weight to be 368.2.
Step (2): the intermediate (I) (150 g,0.407 mol) obtained in the above step was taken and put into a 2L three-necked flask, and methanol (300 g), purified water (150 g) and sodium hydroxide (97.7 g,2.44 mol) were added thereto and stirred under reflux for 16 hours. Methanol was distilled off under reduced pressure. 36% concentrated hydrochloric acid was added dropwise to the aqueous phase until ph=2 to 3, and a white solid was precipitated. Filtration, rinsing the filter cake with purified water, and vacuum drying at 80deg.C for 12 hours, to give 101.4g of intermediate (II) as a white solid with a purity of 99.7% (HPLC), melting point 330.3 ℃. Step (2) molar yield: 96.5%.
Step (3): intermediate (II) (100 g,0.387 mol), dichloroethane (300 mL), thionyl chloride (138.2 g,1.16 mol) and 0.2mL of DMF obtained in the above step were sequentially added to a 2L three-necked flask, and the mixture was heated to reflux and stirred for 3 hours. After the reaction is completed by HPLC (high performance liquid chromatography), the solvent is removed by reduced pressure distillation, and the residue is added with toluene for recrystallization to obtain 109.9g of white crystal finished product with the purity of 99.8 percent (HPLC) and the melting point of 89.9-92.5 ℃. Step (3) molar yield: 96.2%. The total molar yield of the three steps is as follows: 81.1%.
Many possible variations and modifications of the disclosed technology can be made by anyone skilled in the art without departing from the scope of the technology, or the technology can be modified to be equivalent. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention shall still fall within the scope of the technical solution of the present invention.
Claims (9)
1. The preparation method of the 4,4' -diphenyl ether diformyl chloride is characterized by comprising the following steps:
S1, diphenyl ether and carbamoyl chloride or dialkyl carbamoyl chloride are catalyzed by Lewis acid to obtain an intermediate I; wherein the dialkylcarbamoyl chloride comprises dimethylcarbamoyl chloride and diethylcarbamoyl chloride;
s2, hydrolyzing the intermediate I under the action of a hydrolysis reagent to obtain an intermediate II;
S3, performing an acyl chlorination reaction on the intermediate II under the action of an acyl chlorination reagent to obtain the 4,4' -diphenyl ether diformyl chloride.
2. The method for preparing 4,4' -diphenylether dicarboxylic acid dichloride according to claim 1, wherein the molar ratio of diphenylether to carbamoyl chloride is 1:2 to 1:5; the molar ratio of the diphenyl ether to the dialkyl carbamoyl chloride is 1:2-1:5; the molar ratio of the Lewis acid to the diphenyl ether is 2:1-3:1, and the reaction temperature is 20-120 ℃.
3. The method for preparing 4,4' -diphenylether dicarboxylic acid chloride according to claim 1, wherein the lewis acid is one of aluminum chloride, ferric chloride, zinc chloride, manganese chloride and boron trifluoride.
4. The method for preparing 4,4' -diphenylether dicarboxylic acid dichloride according to claim 1, wherein the solvent used in step S1 is one of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, chlorobenzene or dichlorobenzene.
5. The method for preparing 4,4' -diphenyl ether diformyl chloride according to claim 1, wherein the hydrolysis reagent in the step S2 is one of lithium hydroxide, sodium hydroxide or potassium hydroxide, the molar ratio of the intermediate I to the hydrolysis reagent is 1:3-1:20, and the reaction temperature is 20-80 ℃.
6. The method for preparing 4,4' -diphenylether dicarboxylic acid dichloride according to claim 1, wherein the solvent used in step S2 is methanol, ethanol or a mixture of tetrahydrofuran and water.
7. The method for preparing 4,4' -diphenylether dicarboxylic acid dichloride according to claim 1, wherein the acid chloride reagent in step S3 is one of thionyl chloride, oxalyl chloride or triphosgene; the mol ratio of the intermediate II to the acyl chloride reagent is 1:2-1:20, and the acyl chloride reaction temperature is 40-120 ℃.
8. The method for preparing 4,4' -diphenylether dicarboxylic acid dichloride according to claim 1, wherein the solvent used in step S3 is one of toluene, tetrahydrofuran, DMF, dichloromethane and dichloroethane.
9. The method for preparing 4,4' -diphenylether dicarboxylic acid dichloride according to claim 1, comprising the steps of:
S1, adding 1.0mol of diphenyl ether and 850mL of dichloroethane, stirring at 0-5 ℃ while adding 2.4mol of aluminum trichloride, and adding 2.2mol of carbamoyl chloride in portions within 1.5 hours; reacting for 16h at 50 ℃, and cooling to room temperature; 700mL of 12% diluted hydrochloric acid was added at 0deg.C; stirring at room temperature for 20min, standing for layering, washing the obtained organic phase with purified water twice, and distilling under reduced pressure to remove solvent to obtain light yellow oily substance; adding methanol for recrystallization to obtain 4,4' -diphenyl ether dimethylformamide; the batch adding method comprises the steps of controlling the temperature to be 0-5 ℃, stopping adding when the temperature is close to 5 ℃, stirring until the temperature is reduced, and continuing adding;
S2, taking 0.780mol of 4,4' -diphenyl ether dimethylformamide, 500g of methanol, 300g of water and 4.68mol of sodium hydroxide, and stirring at 60 ℃ for 8 hours; removing methanol by reduced pressure distillation; dropwise adding 36% concentrated hydrochloric acid into the water phase until the pH value is=2-3, and precipitating white solid; filtering, and vacuum drying at 80 ℃ for 12 hours to obtain 4,4' -diphenyl ether dicarboxylic acid;
s3, taking 0.697mol of 4,4' -diphenyl ether dicarboxylic acid, 300mL of dichloroethane, 2.09mol of thionyl chloride and 0.2mL of DMF, heating to 83 ℃, refluxing and stirring for 3 hours; removing the solvent by reduced pressure distillation, adding toluene for recrystallization, and obtaining the 4,4' -diphenyl ether diformyl chloride.
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| Structure–activity relationships for 1-alkyl-3-(1-naphthoyl)indoles at the cannabinoid CB1 and CB2 receptors: steric and electronic effects of naphthoyl substituents. New highly selective CB2 receptor agonists;John W. Huffman et al;Bioorganic & Medicinal Chemistry;20041117;第13卷(第2005期);89-112 * |
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