CN106316810A - Preparation method for increasing synthetic yield of 1,1,3-trichloroacetone - Google Patents
Preparation method for increasing synthetic yield of 1,1,3-trichloroacetone Download PDFInfo
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- CN106316810A CN106316810A CN201610590411.XA CN201610590411A CN106316810A CN 106316810 A CN106316810 A CN 106316810A CN 201610590411 A CN201610590411 A CN 201610590411A CN 106316810 A CN106316810 A CN 106316810A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a preparation method for increasing the synthetic yield of 1,1,3-trichloroacetone, and belongs to the technical field of organic synthesis. The method comprises the steps that a load type amine catalyst is prepared, a certain amount of ultra pure acetone is added into a reactor, the load type amine catalyst is slowly added in a stirring state, after the load type amine catalyst and ultra pure acetone are fully mixed to be uniform, temperature is increased, the temperature inside the reactor is controlled to be at 25 DEG C to 30 DGE C, chlorine starts to be introduced into the reactor under the stirring condition, after chlorine introduction is finished, the reaction temperature is controlled to be constant, stirring and thermal reacting continue to be conducted for 2 h, and then 1,1,3-trichloroacetone is obtained. According to the preparation method, the load type amine catalyst is used, the contact area with reactant is increased, the selectivity of 1,1,3-trichloroacetone is improved, and the yield of 1,1,3-trichloroacetone is further increased. According to the load type amine catalyst, load in a covalent bond connection mode is firm, and the catalyst can be recycled multiple times.
Description
Technical field:
The invention belongs to technical field of organic synthesis, be specifically related to a kind of system improving 1,1,3-trichloroacetone synthesis yield
Preparation Method.
Background technology:
1,1,3-trichloroacetone is the important intermediate producing folic acid, and folic acid is also FA, is a kind of water soluble vitamin
Raw element, it is the human body necessary material when utilizing sugar and aminoacid, is also body cell growth and the necessary thing of breeding
Matter.Food containing folic acid is a lot, but due to natural folic acid extremely unstable, is easily affected by the factor such as sunlight, temperature and occur
Oxidation, so the folic acid that human body really can obtain from food is the most few；And the folic acid synthesized can stable for extended periods of time, Yi Beiren
Body absorbs and availability is higher.
At present, domestic production 1,1,3-trichloroacetone main method is acetone direct chlorination method, the production process of the method
In need not add catalyst, but the production cycle need 48h, the poor selectivity of reaction, cause 1, the yield of 1,3-trichloroacetone
Low, the content of 1,1,3-trichloroacetone only accounts for about 17% in the reaction product, and causes producing because it is difficult isolated and purified
Cost is high, and product purity is low.Chinese patent CN90105852.1 discloses a kind of chlorinated with chlorine method synthesis 1,1,3-trichloroacetone,
This synthetic method use single diethylamine or triethylamine make catalyst, although to improve 1, the selection of 1,3-trichloroacetone
Property, but the yield of 1,1,3-trichloroacetone is the most relatively low.At present, domestic production folic acid relatively costly, yield is also difficult to
To improving, these problems cause folic acid product to lose corresponding competitiveness in the international market.Therefore, in order to solve 1,1,3-
Trichloroacetone series of technical present in the large-scale industrial production, the present invention proposes a kind of 1,1,3-trichlorine third
The novel method for synthesizing of ketone, it is an object of the invention to provide a kind of simple to operate, reaction time is short, selectivity good, yield is high and
The synthetic method that purity is good.
Summary of the invention:
The present invention is directed to present in existing 1,1,3-trichloroacetone synthesis technique length reaction time, poor selectivity, productivity
Many technical problems such as low, it is provided that a kind of preparation method improving 1,1,3-trichloroacetone synthesis yield.The inventive method is from urging
Agent angle is set out, and uses the support type amines catalyst that selectivity is good instead, and the preparation method of such catalyst is to use infusion process
Loading to amine organic compound, on nanometer porous silicon, be prepared as support type amines catalyst, porous silica material typically selects
With mesoporous material, pore diameter range is 2～50nm, such as: SBA-15, MCM-41 etc..Reaction raw materials selects ultrapure acetone, necessarily
Working condition under, synthesize 1,1,3-trichloroacetone.
A kind of preparation method improving 1,1,3-trichloroacetone synthesis yield that the present invention provides, concrete reaction equation is such as
Shown in lower:
Specifically comprising the following steps that of the preparation method of a kind of 1,1,3-of raising trichloroacetone synthesis yield provided by the present invention
(1) support type amines catalyst is prepared:
1. (concentrated hydrochloric acid activation modification is mesoporous to add the most activated 120mg molecular sieve SBA-15 in the eggplant type bottle of 50mL
Molecular sieve), eggplant type bottle is put into oil bath pan heating, the temperature in control oil bath pan is at 120 DEG C, continuously stirred, insulation activation 6h,
Molecular sieve SBA-15 after being activated.
2. N2 protect under, in the round-bottomed flask of 50mL add gamma-aminopropyl-triethoxy-silane 12mg (structural formula:) and the dehydrated alcohol 5mL of deoxygenation, or add γ-aminoethylaminopropyl trimethoxy silane 12mg (structure
Formula:) and the dehydrated alcohol 5mL of deoxygenation, stir and obtain gamma-aminopropyl-triethoxy-silane
Mixed solution with deoxygenation dehydrated alcohol or γ-aminoethylaminopropyl trimethoxy silane with deoxygenation dehydrated alcohol.
3. at N2Under protection, under stirring by step 2. described in mixed solution be slowly added to what 1. step obtained
In molecular sieve SBA-15 after described activation, control temperature, at 80 DEG C, is sufficiently stirred for, insulation reaction 20h；After insulation terminates, will
The solid ether being filtrated to get obtains support type amines catalyst after fully washing, and will not load to molecular sieve mesopore surfaces
Organic component washes clean, dry, described support type amines catalyst to be synthesized 1,1,3-trichloroacetone reaction time use.
(2) synthesis 1,1,3-trichloroacetone:
1. adding a certain amount of ultrapure acetone in reactor, be slowly added under stirring that step (1) obtains is negative
Load type amines catalyst, addition is ultrapure acetone the 5 of described support type amines catalyst～10wt%, treat support type amine
After catalyst and ultrapure acetone are sufficiently mixed uniformly, rise high-temperature, control the temperature in reactor at 25～30 DEG C.
2. the temperature stabilization in question response device is when 25～30 DEG C, starts under agitation to be passed through chlorine in reactor
Gas, the mol ratio of described ultrapure acetone and described chlorine is 1:3, is passed through after chlorine terminates, controls reaction temperature constant, continue to stir
Mix, prepare 1,1,3-trichloroacetone after insulation reaction 2h.
According to the difference of each elementary reaction speed of experiment, logical chlorine process is divided into three phases: front 1～2h at the beginning of for reaction
Phase；2～6h for reacting mid-term；6～18h is the reaction later stage.When its initial reaction stage and later stage, response speed is relatively slow, thus logical
The speed entering chlorine is the slowest, controls 6～8L/h；And in the reaction the phase when, response speed is very fast, so needing to strengthen
It is passed through the speed of chlorine, controls 30～32L/h.According to the difference of each elementary reaction speed, we lead to by controlling each stage
Enter the speed of chlorine, can reach the time being passed through chlorine that shortens, the generation of suppression side reaction, improve 1,1, the choosing of 3-trichloroacetone
Selecting property.
The present invention has a techniques below feature:
(1) compared with original single catalyst, support type amines catalyst is used in this test instead, not only increases and reacts
The contact area of thing, raising 1,1, the selectivity of 3-trichloroacetone, and further increase 1, the yield of 1,3-trichloroacetone；
(2) catalyst used is porous silicon loaded catalyst, this catalyst chemical stable in properties, easily stores, to behaviour
Make workshop without too high requirement；
(3) 1,1,3-trichloroacetone synthetic reaction condition is gentle, it is common that 25～30 DEG C, carry out under normal pressure, it is to avoid
The problem that reactor is caused the biggest burden by reaction under high pressure；
(4) the support type amines catalyst that the present invention uses, firm by the load of covalent bond connected mode, catalyst can
It is recycled for multiple times.
Detailed description of the invention:
Embodiment 1: add 232.0g (4.0mol) ultrapure acetone in the reaction bulb of 1000mL, under stirring slowly
Adding the many amines catalysts of 11.6g support type, rise high-temperature with water-bath after stirring, the temperature stabilization in question response bottle exists
When 25 DEG C, starting to be passed through chlorine in reaction bulb and carry out chlorination reaction, it is 6.0L/h that initial reaction stage 1～2h leads to the speed of chlorine,
It is 30.0L/h that mid-term 2～6h leads to the speed of chlorine, and it is 6.0L/h that the later stage 6～20h leads to the speed of chlorine.Chlorine to be led to reaction terminates
After, keep in reaction bulb is temperature-resistant, continues stirring 1～2h.After insulation reaction terminates, keep the temperature in reaction bulb not
Become, in reaction bulb, add a certain amount of special solvent, continuously stirred 1h.After stirring terminates, by obtained mixture ice
Water reduce temperature to 10 DEG C, crystallisation by cooling, the solid that sucking filtration obtains, i.e. 1,1,3-trichloroacetone product.Employing special solvent enters
Row crystallization and purification, product purity is 90.7%, and yield is 46.8%.
Embodiment 2: add 232.0g (4.0mol) ultrapure acetone in the reaction bulb of 1000mL, under stirring slowly
Adding the many amines catalysts of 14.0g support type, rise high-temperature with water-bath after stirring, the temperature stabilization in question response bottle exists
When 30 DEG C, starting to be passed through chlorine in reaction bulb and carry out chlorination reaction, it is 6.0L/h that initial reaction stage 1～2h leads to the speed of chlorine,
It is 32.0L/h that mid-term 2～6h leads to the speed of chlorine, and it is 6.0L/h that the later stage 6～18h leads to the speed of chlorine.Chlorine to be led to reaction terminates
After, keep in reaction bulb is temperature-resistant, continues stirring 1～2h.After insulation reaction terminates, keep the temperature in reaction bulb not
Become, in reaction bulb, add a certain amount of special solvent, continuously stirred 1h.After stirring terminates, by obtained mixture ice
Water reduce temperature to 10 DEG C, crystallisation by cooling, the solid that sucking filtration obtains, i.e. 1,1,3-trichloroacetone product.Employing special solvent enters
Row crystallization and purification, product purity is 94.3%, and yield is 47.4%.
Embodiment 3: add 232.0g (4.0mol) ultrapure acetone in the reaction bulb of 1000mL, under stirring slowly
Adding the many amines catalysts of 21.0g support type, rise high-temperature with water-bath after stirring, the temperature stabilization in question response bottle exists
When 30 DEG C, starting to be passed through chlorine in reaction bulb and carry out chlorination reaction, it is 8.0L/h that initial reaction stage 1～2h leads to the speed of chlorine,
It is 28.0L/h that mid-term 2～6h leads to the speed of chlorine, and it is 8.0L/h that the later stage 6～18h leads to the speed of chlorine.Chlorine to be led to reaction terminates
After, keep in reaction bulb is temperature-resistant, continues stirring 1～2h.After insulation reaction terminates, keep the temperature in reaction bulb not
Become, in reaction bulb, add a certain amount of special solvent, continuously stirred 1h.After stirring terminates, by obtained mixture ice
Water reduce temperature to 10 DEG C, crystallisation by cooling, the solid that sucking filtration obtains, i.e. 1,1,3-trichloroacetone product.Employing special solvent enters
Row crystallization and purification, product purity is 90%, and yield is 48.1%.
Claims (1)
1. the preparation method improving 1,1,3-trichloroacetone synthesis yield, it is characterised in that the method specifically comprises the following steps that
(1) support type amines catalyst is prepared:
1. in the eggplant type bottle of 50mL, add the most activated 120mg molecular sieve SBA-15 (concentrated hydrochloric acid activation modification mesoporous molecular
Sieve), eggplant type bottle is put into oil bath pan heating, the temperature in control oil bath pan is at 120 DEG C, continuously stirred, insulation activation 6h, obtains
Molecular sieve SBA-15 after activation；
2., under N2 protects, in the round-bottomed flask of 50mL, gamma-aminopropyl-triethoxy-silane 12mg and the anhydrous second of deoxygenation are added
Alcohol 5mL or addition γ-aminoethylaminopropyl trimethoxy silane 12mg and deoxygenation dehydrated alcohol 5mL, stirs and obtains
The mixed solution of gamma-aminopropyl-triethoxy-silane or γ-aminoethylaminopropyl trimethoxy silane and deoxygenation dehydrated alcohol；
3. at N2Under protection, under stirring by step 2. described in mixed solution be slowly added to described in 1. step obtain
In molecular sieve SBA-15 after activation, control temperature, at 80 DEG C, is sufficiently stirred for, insulation reaction 20h；After insulation terminates, will filter
The solid ether obtained obtains support type amines catalyst after fully washing；
(2) synthesis 1,1,3-trichloroacetone:
1. in reactor, add a certain amount of ultrapure acetone, under stirring, be slowly added to the support type that step (1) obtains
Amines catalyst, addition is ultrapure acetone the 5 of described support type amines catalyst～10wt%, treat support type amines catalysis
After agent and ultrapure acetone are sufficiently mixed uniformly, rise high-temperature, control the temperature in reactor at 25～30 DEG C；
2. the temperature stabilization in described reactor is when 25～30 DEG C, starts under agitation to be passed through chlorine in reactor
Gas, the mol ratio of described ultrapure acetone and described chlorine is 1:3, is passed through after chlorine terminates, controls reaction temperature constant, continue to stir
Mix, prepare 1,1,3-trichloroacetone after insulation reaction 2h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946676A (en) * | 2017-04-28 | 2017-07-14 | 常州市新鸿医药化工技术有限公司 | A kind of method of purification for being used to prepare the trichloroacetone with high purity of folic acid |
| CN108727173A (en) * | 2017-04-19 | 2018-11-02 | 江西天新药业有限公司 | The method for preparing 1,1,3- trichloroacetones |
| CN113548949A (en) * | 2021-08-27 | 2021-10-26 | 常州新东化工发展有限公司 | Production method of 1,1, 3-trichloroacetone |
| CN115784861A (en) * | 2022-11-04 | 2023-03-14 | 南通市常海食品添加剂有限公司 | Method for producing trichloroacetone by continuous microchannel technology |
| CN116283525A (en) * | 2023-03-30 | 2023-06-23 | 故城县渤海化工有限公司 | Preparation method of 1, 3-trichloroacetone |
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| EP0234503B1 (en) * | 1986-02-20 | 1990-09-12 | Wacker-Chemie GmbH | Process for the preparation of 1,1,3-trichloroacetone |
| CN1047853A (en) * | 1990-07-10 | 1990-12-19 | 中国科学院成都有机化学研究所 | 1,1,3-trichloroacetone preparation method |
| CN101497024A (en) * | 2009-01-15 | 2009-08-05 | 华东理工大学 | CO2 sorbent and preparation method thereof |
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2016
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| EP0234503B1 (en) * | 1986-02-20 | 1990-09-12 | Wacker-Chemie GmbH | Process for the preparation of 1,1,3-trichloroacetone |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727173A (en) * | 2017-04-19 | 2018-11-02 | 江西天新药业有限公司 | The method for preparing 1,1,3- trichloroacetones |
| CN108727173B (en) * | 2017-04-19 | 2021-01-01 | 江西天新药业股份有限公司 | Method for preparing 1,1, 3-trichloroacetone |
| CN106946676A (en) * | 2017-04-28 | 2017-07-14 | 常州市新鸿医药化工技术有限公司 | A kind of method of purification for being used to prepare the trichloroacetone with high purity of folic acid |
| 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 |
| CN113548949A (en) * | 2021-08-27 | 2021-10-26 | 常州新东化工发展有限公司 | Production method of 1,1, 3-trichloroacetone |
| CN115784861A (en) * | 2022-11-04 | 2023-03-14 | 南通市常海食品添加剂有限公司 | Method for producing trichloroacetone by continuous microchannel technology |
| WO2024092894A1 (en) * | 2022-11-04 | 2024-05-10 | 南通市常海食品添加剂有限公司 | Method for producing trichloroacetone by means of continuous microchannel technology |
| CN116283525A (en) * | 2023-03-30 | 2023-06-23 | 故城县渤海化工有限公司 | Preparation method of 1, 3-trichloroacetone |
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