CN1018639B - Preparation method of 1, 1, 3-trichloroacetone - Google Patents
Preparation method of 1, 1, 3-trichloroacetoneInfo
- Publication number
- CN1018639B CN1018639B CN 90105852 CN90105852A CN1018639B CN 1018639 B CN1018639 B CN 1018639B CN 90105852 CN90105852 CN 90105852 CN 90105852 A CN90105852 A CN 90105852A CN 1018639 B CN1018639 B CN 1018639B
- Authority
- CN
- China
- Prior art keywords
- acetone
- trichloroacetone
- chlorination reaction
- absorption liquid
- water absorption
- 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.)
- Expired
Links
- ZWILTCXCTVMANU-UHFFFAOYSA-N 1,1,3-trichloropropan-2-one Chemical compound ClCC(=O)C(Cl)Cl ZWILTCXCTVMANU-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003809 water extraction Methods 0.000 claims description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229960000304 folic acid Drugs 0.000 description 4
- 235000019152 folic acid Nutrition 0.000 description 4
- 239000011724 folic acid Substances 0.000 description 4
- MSTNYGQPCMXVAQ-KIYNQFGBSA-N 5,6,7,8-tetrahydrofolic acid Chemical compound N1C=2C(=O)NC(N)=NC=2NCC1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 MSTNYGQPCMXVAQ-KIYNQFGBSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 206010002065 Anaemia megaloblastic Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000000682 Megaloblastic Anemia Diseases 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 231100001016 megaloblastic anemia Toxicity 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing 1, 1, 3-trichloroacetone by catalytic chlorination of acetone. The catalyst can be triethylamine, diethylamine or water absorption liquid of acetone chlorination tail gas, the chlorination reaction temperature is 10-90 deg.C, and the reaction time is 10-20 hr. The method has the advantages of easily controlled production process conditions and safe operation, can shorten the production period of the 1, 1, 3-trichloroacetone produced at present in China by more than half, and improves the selectivity of the product prepared by the method from about 17 percent to 40 to 50 percent.
Description
The present invention relates to a kind of can be used as that folic acid (VBC) raw materials for production use 1,1, the preparation method of 3-trichloroacetone.
Folic acid (VBC) is reducible one-tenth tetrahydrofolic acid (THFA) in tissues such as liver, intestines wall, marrow, and is very active in human body, is the coenzyme of carbon-based group transferring enzyme system, plays a carbon-based group transfer function.Human body lacks folic acid, can cause erythrocytic growth and anacmesis, produces megaloblastic anemia.About 1,1, the method for making of 3-trichloroacetone, it is catalyzer that russian patent (226586,1968) discloses the employing pyridine, makes 1,1, the 3-trichloroacetone with acetone catalytic chlorination method.This method mainly has difficult control of reaction conditions, and at the chlorination reaction initial stage, condition is grasped bad, the danger of easily blasting.Russian patent (224385,1970) is to adopt aminated compounds [H-
-CH3, (C2H5)
2NCH3, (C6H5) NC2H5] be catalyzer, make 1,1 with the acetone catalytic chlorination, the 3-trichloroacetone.This method the explosion hazard that the chlorination reaction initial stage may occur can not occur, but used catalyzer (as previously mentioned) is difficult for obtaining.Domestic production 1,1 at present, 3-trichloroacetone are to adopt the acetone direct chlorination.This method is without catalyzer, but the production cycle reach 48 hours, reaction product after chloracetone is removed in underpressure distillation 1,1, the content of 3-trichloroacetone only is about 17%, long reaction time, poor selectivity are the main drawbacks of this method.Therefore also cause the domestic folic acid production cycle to increase problems such as cost up.
The purpose of this invention is to provide a kind ofly keep the safety in production, easy to implement, not only the reaction times is short but also selectivity is good 1,1, the preparation method of 3-trichloroacetone.
The object of the present invention is achieved like this: in reaction vessel, add amount of acetone and catalyzer, through stirring and evenly mixing, feeding chlorine reacts and makes and wherein contain 1,1, the acetone muriate of 3-trichloroacetone, purify with water extraction again and make 1,1, the 3-trichloroacetone.This preparation method's characteristics are that the catalyzer of employing is triethylamine or the diethylamine for acetone weight 0.5-5%, or be the water absorption liquid of acetone chlorination reaction tail gas of the 10-50% of acetone weight, in this water absorption liquid, in hydrogenchloride, its content is 20-32%, under temperature 10-90 ℃, feed chlorine and carry out chlorination reaction, 10-20 hour chlorination reaction time.
The inventive method is carried out under normal pressure, and manufacturing condition is simple, is easy to control, explosion phenomenon can not occur.The catalyzer that is adopted is easy to obtain and is more inexpensive, and the water absorption liquid that particularly adopts the acetone chlorinated exhaust has the meaning of changing waste into valuable as catalyzer.The inventive method produces 1,1, and the 3-trichloroacetone is compared with domestic production, and the production cycle shortens over half, and selectivity is brought up to 40-50% by about 17%.
The invention will be further described below in conjunction with embodiment:
Can in several placed in-line semi-batch stirred-tank reactors, add acetone and catalyzer earlier,, pass to chlorine again and carry out the acetone chlorination reaction through abundant stirring and evenly mixing.Catalyzer can adopt triethylamine or diethylamine, and its 0.8-1.5% that measures for acetone (weight) with (weight) amount is preferable, or is the water absorption liquid of the acetone chlorination reaction tail gas of acetone weight 10-50%, at this moment, in this water absorption liquid, in hydrogen chloride gas, its content is 32%.The optimal selection of acetone chlorination reaction temperature is 25-30 ℃.In the acetone chlorination reaction, the flow of chlorine is advisable with content ≯ 10% of chlorine in the tail gas, and available water-bath or ice-water bath come the conditioned reaction temperature.Reaction times 10-20 hour.Reactor can adopt enamel still or inwall to be lined with the corrosion resistant reactor of glass.
Embodiment 1: in the three-necked bottle of dribbling shape (or snakelike) prolong, thermometer and the agitator of 250ml, add 116.2 gram acetone and 1.2 gram triethylamine or diethylamine earlier, behind stirring and evenly mixing, feed chlorine and carry out chlorination reaction, all can at 25-35 ℃ to answer temperature.Stopped reaction after 12 hours is carried out in reaction.Reaction product gets 1,1 through water extraction, the 3-trichloroacetone.In the reaction product 1,1,3-trichloroacetone content is 51.9%.
Embodiment 2: with the identical device of embodiment 1, the water absorption liquid that adds 116.2 gram acetone and 12 gram acetone chlorination reaction tail gas earlier, logical chlorine behind stirring and evenly mixing, temperature of reaction all can at 40-70 ℃, stopped reaction after 10 hours is carried out in reaction, in the assaying reaction product organic phase 1,1, the content of 3-trichloroacetone is 41%, in the present embodiment, in the acetone chlorination reaction tail gas water absorption liquid as catalyzer, in hydrogenchloride, content is 32%.
Claims (3)
1, a kind of 1,1,3-trichloroacetone preparation method, this method is in reaction vessel, adds acetone and catalyzer, through stirring and evenly mixing, feeding chlorine carries out chlorination reaction and makes and wherein contain 1,1,3-trichloroacetone muriate is purified with water extraction and is made 1,1, the 3-trichloroacetone, the catalyzer that it is characterized in that this preparation method employing is the water absorption liquid for the acetone chlorination reaction tail gas of acetone weight 10-50%, in this water absorption liquid, in hydrogenchloride, its content is 20-32%, feeds chlorine down at temperature 10-90 ℃ and carries out chlorination reaction, 10-20 hour chlorination reaction time.
2, method according to claim 1 is characterized in that the preferable amount of the water absorption liquid of the catalyzer acetone chlorination reaction tail gas that adopts is the 10-30% of acetone weight, and in this water absorption liquid, in hydrogenchloride, preferred content is 32%.
3, method according to claim 1 and 2 is characterized in that feeding chlorine and carry out chlorination reaction under 40-70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105852 CN1018639B (en) | 1990-07-10 | 1990-07-10 | Preparation method of 1, 1, 3-trichloroacetone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90105852 CN1018639B (en) | 1990-07-10 | 1990-07-10 | Preparation method of 1, 1, 3-trichloroacetone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1047853A CN1047853A (en) | 1990-12-19 |
| CN1018639B true CN1018639B (en) | 1992-10-14 |
Family
ID=4879653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90105852 Expired CN1018639B (en) | 1990-07-10 | 1990-07-10 | Preparation method of 1, 1, 3-trichloroacetone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018639B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768066B (en) * | 2008-12-31 | 2013-04-03 | 上海华理生物医药有限公司 | Preparation method and application of trichloroacetone with high purity |
| CN106316810B (en) * | 2016-07-25 | 2018-08-31 | 安徽千和新材料科技发展有限公司 | A kind of preparation method improving 1,1,3- trichloroacetone synthesis yields |
| CN106542979A (en) * | 2016-10-27 | 2017-03-29 | 黄冈师范学院 | A kind of high-selectivity synthesis method of 1,1,3 trichloroacetone |
| CN106946676B (en) * | 2017-04-28 | 2020-07-17 | 常州市新鸿医药化工技术有限公司 | Purification method of high-purity trichloroacetone for preparing folic acid |
| CN109516908A (en) * | 2017-09-19 | 2019-03-26 | 江西天新药业有限公司 | The method of purification and its application of 1,1,3- trichloroacetone |
| CN107602364B (en) * | 2017-09-26 | 2020-06-05 | 安徽国星生物化学有限公司 | Method for preparing 1,1, 3-trichloroacetone by chlorination of acetone |
| CN113548949B (en) * | 2021-08-27 | 2023-04-18 | 常州新东化工发展有限公司 | Production method of 1,1,3-trichloroacetone |
| CN115784861B (en) * | 2022-11-04 | 2024-06-18 | 南通市常海食品添加剂有限公司 | Method for producing trichloroacetone by continuous microchannel technology |
-
1990
- 1990-07-10 CN CN 90105852 patent/CN1018639B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1047853A (en) | 1990-12-19 |
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Legal Events
| Date | Code | Title | Description |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |