CN1106375A - Synthetic process of triethyl orthoformate - Google Patents
Synthetic process of triethyl orthoformate Download PDFInfo
- Publication number
- CN1106375A CN1106375A CN 94115942 CN94115942A CN1106375A CN 1106375 A CN1106375 A CN 1106375A CN 94115942 CN94115942 CN 94115942 CN 94115942 A CN94115942 A CN 94115942A CN 1106375 A CN1106375 A CN 1106375A
- Authority
- CN
- China
- Prior art keywords
- ethanol
- triethyl orthoformate
- sodium hydroxide
- entrainer
- chloroform
- 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
- 238000000034 method Methods 0.000 title claims abstract description 21
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000012046 mixed solvent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000005911 haloform reaction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- HWJPHQNEWARZLH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5-decafluoro-6,6-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F HWJPHQNEWARZLH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The process for synthesizing triethyl orthoformate features that the pH value is controlled up to 7-10 during all the reaction procedure of sodium hydroxide with chloroform by dropwise adding alcohol timely and controlling proportion of materials, and a scientific washing method is used in separation refining stage to reuse azeotropic agent. Its advantages include high purity up to 98-99%, less raw material consumption and high yield up to 65-75% or more.
Description
Synthetic process of triethyl orthoformate of the present invention belongs to the organic chemical industry field, is specifically related to a kind of organic synthesis technology of producing ortho-formiate.
The technology of domestic and international disclosed production ortho-formiate mainly contains at present:
1.JP 58225036
Methyl alcohol (or ethanol) and sodium hydroxide, haloform reaction add ortho-formiate extraction agent (aliphatic hydrocarbon, aromatic hydrocarbons, ether or halohydrocarbon) in resultant of reaction, also can add extraction agent in step of reaction sometimes, then separation, rectifying.Only relate to trimethyl orthoformate among the embodiment, do not relate to triethyl orthoformate.
2.JP 59001435
Methyl alcohol (or ethanol) and sodium hydroxide, haloform reaction separate salt, and the fractionation by distillation product according to synthetic liquid gas chromatographic analysis, is that benchmark calculates with sodium hydroxide, and yield is 61.2%, reacts 12 hours.
3.CN 1068103A
Methyl alcohol (or ethanol) and sodium hydroxide, haloform reaction add reaction medium (aliphatic hydrocarbon, aromatic hydrocarbons, halohydrocarbon) simultaneously in reactant, separate salt, the fractionation by distillation product.Calculate to react used alcohol, yield is 50-55%.
All there is the ruined problem of ortho-formiate hydrolysis in reaction and the sepn process in technology in sum, so the starting material unit consumption is big, yield is low.
Synthetic process of triethyl orthoformate of the present invention, be intended to solve the ruined gordian technique difficult problem of ortho-formiate hydrolysis in the triethyl orthoformate production technique, and optimizing materials proportioning, improve processing condition, reach and reduce the starting material unit consumption, improve the purity of yield and product, the purpose of increase economic benefit.
Synthetic process of triethyl orthoformate of the present invention drops into sodium hydroxide, chloroform and ethanol by equivalence ratio, it is characterized in that:
I. adding the alcoholic acid mode is regularly to drip, and its fix time is 10-90 minute, and it is hot ethanol that institute adds ethanol, and its temperature is 10-60 ℃.
II. control proportioning raw materials (mol ratio)
Ethanol: sodium hydroxide: chloroform=28～50: 30～48: 12～25, and to become ester reaction whole process acidity of medium be PH=7-14, promptly reacts whole process and all carry out in alkaline medium.
III. add an amount of mixed solvent as entrainer in synthetic liquid, entrainer also can add in initial reaction stage.
IV. washing
Washing times 1～3 time,
10～45 ℃ of wash temperatures,
The bath water amount is 1～5 times of pure material amount,
Washing is stirred 0.1～30 minute time of trembling,
10～90 minutes standing demix time,
Then concentrate, can to obtain purity be triethyl orthoformate 98% or more in rectifying, recyclable solvent of washing water and salt, the mixed solvent that reclaims in the concentrated rectifying can be used as entrainer to be continued to recycle.
Synthetic process of triethyl orthoformate of the present invention, owing to changed feed way, material proportion and potential of hydrogen have been controlled, adopted the washing methods of science, so in reaction and treating process, the hydrolysis that has all suppressed ortho ester effectively destroys, and has guaranteed higher yield, and product purity is reached more than 98%, and stablize and do not decompose, the more important thing is and to reclaim byproduct, and mixed solvent is recycled as entrainer, thereby reduced the starting material unit consumption, improved economic benefit, its whole technological process is simple, and safe and reliable, and the facility investment of equal scale only is half of two step synthesis techniques in the past.
Embodiment 1
Sodium hydroxide 37g is joined in mixed solvent (foreshot of this technology rectifying separation) system of 60g chloroform and 140g, and temperature of charge drips ethanol 48.5g in the time of 25 ℃, 50 ℃ of insulation reaction 1 hour.Synthetic liquid by analysis, to react used alcohol, yield is 65%.
Embodiment 2
In mixed solvent (same precedent) system of 72g chloroform and 168g, add sodium hydroxide 49g, when 20 ℃ of temperature of charge, add ethanol 48.5g gradually, 30 ℃ of insulation reaction 1.5 hours.Reaction is synthesized liquid by analysis, and to react used alcohol, yield is 70%.
Embodiment 3
In 70g chloroform and 300g mixed solvent (same precedent) system, add sodium hydroxide 81g, during 24 ℃ of temperature of charge, in 30 minutes, drip ethanol 80g, insulation reaction is 1.5 hours under the room temperature.Add water 300g in the synthetic liquid, separate dissolved salt, washing back, and secondary adds water 170g again, and separate the washing back, the synthetic liquid after the washing through concentrate, to make purity be 98% triethyl orthoformate product in rectifying.To react used alcohol, yield is 65%.
Implement 4
In 170g chloroform and mixed solvent (same precedent) system of 400g, add sodium hydroxide 125g, add hot ethanol 126g in half an hour gradually, back flow reaction 2 hours.Synthetic liquid is analyzed triethyl orthoformate content after twice washing, to react used alcohol, yield is 75%.
Embodiment 5
Sodium hydroxide 14g joins in 18g chloroform and 40g mixed solvent (same precedent) system, once adds ethanol 20g, back flow reaction 3 hours.Synthetic liquid separates the back and measures triethyl orthoformate content, and yield is that 65%(is to react used alcohol meter).
Claims (1)
- A kind of production synthetic process of triethyl orthoformate drops into sodium hydroxide, chloroform and ethanol by equivalence ratio, it is characterized in that:I. adding the alcoholic acid mode is regularly to drip, and it is fixed time is 10～90 minutes, and it is hot ethanol that institute adds ethanol, and its temperature is 10～60 ℃.II. the control proportioning raw materials according to mol ratio calculating is:Ethanol: sodium hydroxide: chloroform=28～50: 30～48: 12～25, and to become ester reaction whole process acidity of medium be PH=7～14, promptly reacts whole process and all carry out in alkaline medium,III. add an amount of mixed solvent as entrainer in synthetic liquid, entrainer also can add in initial reaction stage,IV. washingWashing times 1～3 time,10～45 ℃ of wash temperatures,The bath water amount is 1～5 times of pure material amount,0.1～30 minute wash agitation time,10～90 minutes standing demix time,Then concentrate, can to obtain purity be triethyl orthoformate product 98% or more in rectifying, recyclable solvent of washing water and salt, the mixed solvent that reclaims in the concentrated rectifying can be used as entrainer to be continued to recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115942A CN1033854C (en) | 1994-09-01 | 1994-09-01 | Synthetic process of triethyl orthoformate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115942A CN1033854C (en) | 1994-09-01 | 1994-09-01 | Synthetic process of triethyl orthoformate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1106375A true CN1106375A (en) | 1995-08-09 |
| CN1033854C CN1033854C (en) | 1997-01-22 |
Family
ID=5037734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94115942A Expired - Fee Related CN1033854C (en) | 1994-09-01 | 1994-09-01 | Synthetic process of triethyl orthoformate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033854C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6281392B1 (en) | 1998-11-18 | 2001-08-28 | Basf Aktiengesellschaft | Preparation of orthoesters |
| CN101817506A (en) * | 2010-03-22 | 2010-09-01 | 临沭县华盛化工有限公司 | Method for purifying hydrogen chloride gas used in production of triethyl orthoformate |
| CN103254046A (en) * | 2013-05-07 | 2013-08-21 | 南京工业大学 | Method for preparing orthoesters by phase transfer catalysis method in microstructure reactor |
| CN105037113A (en) * | 2015-05-29 | 2015-11-11 | 盐城凯利药业有限公司 | Synthesis method of carbonic acid ortho-ester |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS591435A (en) * | 1982-02-23 | 1984-01-06 | Mitsubishi Gas Chem Co Inc | Preparation of orthoformic acid trimethyl or triethyl ester |
| JPS58225036A (en) * | 1982-06-24 | 1983-12-27 | Mitsubishi Gas Chem Co Inc | Production of trimethyl or triethyl orthoformate |
| CN1034659C (en) * | 1992-07-01 | 1997-04-23 | 南通长江化学有限公司 | One-step synthesis of ortho-formate |
-
1994
- 1994-09-01 CN CN94115942A patent/CN1033854C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6281392B1 (en) | 1998-11-18 | 2001-08-28 | Basf Aktiengesellschaft | Preparation of orthoesters |
| CN101817506A (en) * | 2010-03-22 | 2010-09-01 | 临沭县华盛化工有限公司 | Method for purifying hydrogen chloride gas used in production of triethyl orthoformate |
| CN101817506B (en) * | 2010-03-22 | 2011-07-20 | 临沭县华盛化工有限公司 | Method for purifying hydrogen chloride gas used in production of triethyl orthoformate |
| CN103254046A (en) * | 2013-05-07 | 2013-08-21 | 南京工业大学 | Method for preparing orthoesters by phase transfer catalysis method in microstructure reactor |
| CN105037113A (en) * | 2015-05-29 | 2015-11-11 | 盐城凯利药业有限公司 | Synthesis method of carbonic acid ortho-ester |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1033854C (en) | 1997-01-22 |
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