CN1611480A - Acetoxy acetyl chloride puritying method - Google Patents
Acetoxy acetyl chloride puritying method Download PDFInfo
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- CN1611480A CN1611480A CN 200310110808 CN200310110808A CN1611480A CN 1611480 A CN1611480 A CN 1611480A CN 200310110808 CN200310110808 CN 200310110808 CN 200310110808 A CN200310110808 A CN 200310110808A CN 1611480 A CN1611480 A CN 1611480A
- Authority
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- China
- Prior art keywords
- alpha
- solvent
- purification process
- chloride
- acetoxyacetyl chloride
- 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.)
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- HZDNNJABYXNPPV-UHFFFAOYSA-N (2-chloro-2-oxoethyl) acetate Chemical compound CC(=O)OCC(Cl)=O HZDNNJABYXNPPV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 15
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005917 acylation reaction Methods 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 2
- -1 acetone Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 150000001555 benzenes Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- MLXDUYUQINCFFV-UHFFFAOYSA-N 2-acetyloxyacetic acid Chemical compound CC(=O)OCC(O)=O MLXDUYUQINCFFV-UHFFFAOYSA-N 0.000 abstract 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000010606 normalization Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229960003320 roxatidine Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SMTZFNFIKUPEJC-UHFFFAOYSA-N Roxane Chemical compound CC(=O)OCC(=O)NCCCOC1=CC=CC(CN2CCCCC2)=C1 SMTZFNFIKUPEJC-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a kind of treatment method for purification of acetoxyl acetyl chloride. Get reaction product by chlorination reaction with acetoxyl acetic acid, and then remove the excessive chlorination agent used in the reaction and acetyl chloride generated possibly by distillation. After, add solvent with 50-150deg.C boiling-point and with inertia to reaction product, then go on to remove surviving acetyl chlorine and added solvent completely by distillation. Finally, collect acetyl oxygen-group acetyl chlorine product with cut fraction of 53-56deg.C/12mmHg by under pressure distillation.
Description
Technical field
What the present invention relates to is a kind of purification process that is used for alpha-Acetoxyacetyl chloride.
Background technology
Alpha-Acetoxyacetyl chloride (CH
3COOCH
2COCl) be the intermediate of a Minute Organic Synthesis, as synthetic intermediate as medicine roxatidine and analogue.In the preparation method of routine; as the acetoxy acid chloro being got with thionyl chloride, phosphorus pentachloride etc.: owing to often be mixed with a spot of Mono Chloro Acetic Acid, acetate in the acetoxy acid, so may have impurity such as a spot of chloroacetyl chloride, Acetyl Chloride 98Min. in the chloro-product.Because the chemically reactive of these impurity is bigger, must remove, to guarantee the purity of next step synthetic product.In general the application, these impurity do not have much influences; But, just may cause the content of related substances higher to as in the higher medicine of ask for something purity such as roxatidine synthetic.Although more available process for purification are removed related substances, to guarantee quality as these medicines such as roxatidine acetates.But adopt highly purified alpha-Acetoxyacetyl chloride, the generation that reduces impurity should be a suitable commercial run.In the purifying of alpha-Acetoxyacetyl chloride preparation, ordinary method can adopt the method for rectifying, but the equipment requirements of rectifying is higher, and energy expenditure is bigger, complex operation.
Summary of the invention
At above-mentioned situation, it is a kind of to alpha-Acetoxyacetyl chloride purification treating method comparatively easily that the present invention will provide, and can avoid tradition to adopt the mode of rectifying, reduces the input of equipment and the consumption of the energy, and make simplified control.
Alpha-Acetoxyacetyl chloride purification process of the present invention, be to behind chlorination, obtaining reaction product by acetoxy acid, earlier with the distillation mode remove the used excess chlorine of dereaction for agent and issuable Acetyl Chloride 98Min. after, add boiling point again and be 50 ℃～150 ℃ and reaction product is the inert solvent, continuation eliminates remaining Acetyl Chloride 98Min. and the solvent that is added in the distillation mode, collect the alpha-Acetoxyacetyl chloride product of 53 ℃～56 ℃/12mmHg scope cut at last in the underpressure distillation mode, can obtain the higher alpha-Acetoxyacetyl chloride of purity.
Because in the report of the method for preparing acetoxy acid through the chloro acylation reaction; at most and the chloro agent of the most normal use generally be adopted as thionyl chloride more; therefore, said herein generally being can be understood as by the chloro agent that should be distilled away in the reacted product mixtures mainly is meant as chlorinating agents commonly used such as thionyl chlorides.
In above-mentioned purification process, when steam removing the inert solvent that said excess chlorine adds for agent and issuable Acetyl Chloride 98Min., operable satisfactory inert solvent, the aromatic solvent as benzene classes such as toluene that can have very high inertia performance in the ordinary course of things, or in as Skellysolve A, normal hexane, hexanaphthene, chloroform equal solvent at least a fat hydrocarbon solvent, or in as tetrahydrofuran (THF), dioxane equal solvent at least a ether solvent, or in as acetone, butanone equal solvent, select for use at least a ketones solvent.These inert solvents both can adopt the form of single solvent to use, or adopted the mode of mixed solvent to be used.And the solvent that distills out can also be used repeatedly.
Above-mentioned purification process of the present invention is compared with the rectifying mode that present conventional report uses, and does not need to increase rectifying device, and simple to operate, and energy consumption is also few.
According to foregoing,,, can also make modification, replacement or the change of various ways according to the ordinary skill knowledge and the customary means of this area not breaking away under the above-mentioned basic fundamental thought of the present invention prerequisite.
The embodiment of form is described in further detail foregoing of the present invention again by the following examples.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment
Example 1
After 118g (1mol) acetoxy acid and 120ml (1.65mol) thionyl chloride, 100ml Acetyl Chloride 98Min. stirring and refluxing carried out chlorination in 2 hours, air distillation is removed excess chlorine for agent and issuable Acetyl Chloride 98Min., add chloroform 100ml again, air distillation does not distillate to there being chloroform, 53 ℃～56 ℃/12mmHg scope cut is collected in underpressure distillation then, obtain the alpha-Acetoxyacetyl chloride product 98.3g of purifying, yield 72%.To collected product gas chromatographic analysis, and detect its content with normalization method, the content of alpha-Acetoxyacetyl chloride is 99.3%.
Example 2
After 118g (1mol) acetoxy acid and 120ml (1.65mol) thionyl chloride, 100ml Acetyl Chloride 98Min. stirring and refluxing carried out acylation reaction in 3 hours; after low boilers is removed in the same manner air distillation; adding toluene 100ml; air distillation does not distillate to there being toluene; 53 ℃～56 ℃/12mmHg scope cut is collected in underpressure distillation; obtain the alpha-Acetoxyacetyl chloride 97g of purifying, yield 71%.To collected product gas chromatographic analysis and normalization method detection level, the content of alpha-Acetoxyacetyl chloride is 99.2%.
Example 3
After 118g (1mol) acetoxy acid and 120ml (1.65mol) thionyl chloride, 100ml Acetyl Chloride 98Min. stirring and refluxing carried out the chloro acylation reaction in 3 hours; remove low boilers by above-mentioned with the quadrat method air distillation; add tetrahydrofuran (THF) 100ml again; air distillation does not distillate to there being tetrahydrofuran (THF); 53 ℃～56 ℃/12mmHg scope cut is collected in underpressure distillation again; obtain the alpha-Acetoxyacetyl chloride product 100g of purifying, yield 73%.To collected product gas chromatographic analysis and normalization method detection level, the content of alpha-Acetoxyacetyl chloride is 99.3%.
Claims (7)
1. the purification process of alpha-Acetoxyacetyl chloride, it is characterized in that behind chlorination, obtaining reaction product by acetoxy acid, earlier with the distillation mode remove the used excess chlorine of dereaction for agent and issuable Acetyl Chloride 98Min. after, add boiling point again and be 50 ℃～150 ℃ and reaction product is the inert solvent, continuation eliminates remaining Acetyl Chloride 98Min. and the solvent that is added in the distillation mode, collects the alpha-Acetoxyacetyl chloride product of 53 ℃～56 ℃/12mmHg scope cut at last in the underpressure distillation mode.
2. the purification process of alpha-Acetoxyacetyl chloride as claimed in claim 1, the inert solvent that it is characterized in that said adding are at least a in aromatic hydrocarbons such as benzene class, fat hydrocarbon, ethers or the ketones solvent.
3. the purification process of alpha-Acetoxyacetyl chloride as claimed in claim 1 is characterized in that said benzene kind solvent is a toluene.
4. the purification process of alpha-Acetoxyacetyl chloride as claimed in claim 1 is characterized in that said fat hydrocarbon solvent is at least a in Skellysolve A, normal hexane, hexanaphthene, sherwood oil, the chloroform.
5. the purification process of alpha-Acetoxyacetyl chloride as claimed in claim 1 is characterized in that said ether solvent is at least a in tetrahydrofuran (THF), the dioxane.
6. the purification process of alpha-Acetoxyacetyl chloride as claimed in claim 1 is characterized in that said ketones solvent is at least a in ketone such as acetone, the butanone.
7. as the purification process of the described alpha-Acetoxyacetyl chloride of one of claim 1 to 6, it is characterized in that the acylating agent that chloro acylation reaction that said distillation is gone out is used is a thionyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310110808 CN1611480A (en) | 2003-10-29 | 2003-10-29 | Acetoxy acetyl chloride puritying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310110808 CN1611480A (en) | 2003-10-29 | 2003-10-29 | Acetoxy acetyl chloride puritying method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1611480A true CN1611480A (en) | 2005-05-04 |
Family
ID=34759239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310110808 Pending CN1611480A (en) | 2003-10-29 | 2003-10-29 | Acetoxy acetyl chloride puritying method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1611480A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935852A (en) * | 2017-11-29 | 2018-04-20 | 盐城师范学院 | A kind of chemical synthesis process of acetoxy acetyl chloride |
-
2003
- 2003-10-29 CN CN 200310110808 patent/CN1611480A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107935852A (en) * | 2017-11-29 | 2018-04-20 | 盐城师范学院 | A kind of chemical synthesis process of acetoxy acetyl chloride |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |