CN105254488A - Synthesis method for stearoyl chloride - Google Patents
Synthesis method for stearoyl chloride Download PDFInfo
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- CN105254488A CN105254488A CN201510705451.XA CN201510705451A CN105254488A CN 105254488 A CN105254488 A CN 105254488A CN 201510705451 A CN201510705451 A CN 201510705451A CN 105254488 A CN105254488 A CN 105254488A
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- CN
- China
- Prior art keywords
- stearic acid
- acid chloride
- synthetic method
- conducting
- reaction
- 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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- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000001308 synthesis method Methods 0.000 title abstract 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008117 stearic acid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- -1 chloride sulfoxide Chemical class 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 14
- 238000010992 reflux Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 238000003756 stirring Methods 0.000 abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- 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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method for stearoyl chloride. The method includes the steps of firstly, mixing stearic acid and water according to the weight part ratio of 100 to 1, dropwise adding thionyl chloride at the temperature of 0-5 DEG C, conducting stirring while dropwise adding is conducted, adding N,N-dimethylformamide to serve as catalysts after dropwise adding is finished, raising the temperature to 85-95 DEG C, conducting a reflux reaction for 2 h, processing reaction tail gas through a tail gas processing device, conducting reactions till no gas is discharged, and conducting cooling to separate out crude stearoyl chloride products; secondly, conducting distillation and purification on the crude stearoyl chloride products which are separated out under the conditions that the vacuum degree is 730-840 mmHg and the temperature is 120-140 DEG C, and recycling remaining thionyl chloride and catalysts to obtain stearoyl chloride. The method is few in by-product, high in product purity, easy to operate, short in reaction time and little in environment pollution.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to a kind of synthetic method of stearic acid chloride.
Background technology
Acyl chlorides is a kind of important carboxylic acid derivative, and in organic synthesis, there is important application the aspects such as pharmaceutical synthesis, mainly can be hydrolyzed, alcoholysis, aminolysis, react with organometallic reagent and the multiple reaction such as reduction reaction, have research much related to this to be devoted to the synthesis of acyl chlorides.Stearic acid chloride is the important Organic Chemicals of a class, is generated by straight-chain carboxylic acid's chloride, the main synthesis being used as the sizing agent alkyl ketene dimer (AKD) of paper making pulp, is also widely used in the synthesis of doctor material, dyestuff, tensio-active agent etc.Prepare the production technique of stearic acid chloride at present mainly based on gas phase phosgenation method and liquid phase light phosgenation, but the complex process of phosgenation, troublesome poeration, super toxicity makes it be subject to huge application in actual applications.
Summary of the invention
The object of the invention is to avoid the deficiencies in the prior art, provide that a kind of technique is simple, easy to operate, product yield and the high and excessive recyclable recycling of sulfur oxychloride of purity.
To achieve these goals, the technical scheme that the present invention takes is:
A synthetic method for stearic acid chloride, comprises the steps:
Step one: by stearic acid and water 100:1 mixing by weight, sulfur oxychloride is dripped under adding at 0-5 DEG C, dropping limit, limit is stirred, and drips after terminating, adds N, dinethylformamide makees catalyzer, be warming up to 85-95 DEG C of back flow reaction 2h, reaction end gas carries out vent gas treatment by exhaust gas processing device, and reaction terminates to releasing without gas, cooling, separates out the thick product of stearic acid chloride; Step 2: be 730-840mmHg in vacuum tightness by thick for precipitation stearic acid chloride product, temperature is carry out distilation under the condition of 120-140 DEG C, by residual chloride sulfoxide and catalyst recovery, obtains stearic acid chloride; Sulfur oxychloride, as solvent, interacts owing to existing between sulfur oxychloride and stearic acid chloride, and conventional vacuum distillation is difficult to it to remove from reaction, causes producing byproduct, produces impurity, thus affect quality product.
In described step one, first vent gas treatment is separated SO in order under cryogenic condensation device
2, then absorb HCl gas by NaOH solution.
The mass ratio of described stearic acid and sulfur oxychloride is 1:1.8-3.
The mass ratio of described stearic acid and catalyzer is 1:0.5-1.2%, and in reaction process, the amount of catalyzer cannot be too many, if the amount of catalyzer is too much, excessive catalyzer will react with the stearic acid chloride generated.
Described catalyzer is can also be any one in N,N-dimethylacetamide, triethylamine, pyridine, cetyl trimethylammonium bromide.
Reaction principle is:
Described catalyst levels is the 0.5-1.2% of stearic acid quality, and in reaction process, the amount of catalyzer cannot be too many, if the amount of catalyzer is too much, excessive catalyzer will react with the stearic acid chloride generated,
Beneficial effect of the present invention is:
1. this synthetic method, by product is few, and product purity is high, the HCl of generation, SO
2gas can be absorbed and used, and is a kind of stearic acid chloride production technique of high-efficiency environment friendly high-quality.
2. under the condition of 730-840mmHg and 120-140 DEG C, carry out the thick product distilation of stearic acid chloride, effectively can remove the sulfur oxychloride in reaction solution and catalyzer, shorten the distilation time, avoid the generation of by product, improve purity and the yield of product.
Embodiment
Below by the description to embodiment, next the present invention is further detailed explanation.
Reagent used in the embodiment of the present invention is commercially available.
Embodiment 1:
By 10g stearic acid, 0.10g water adds in the there-necked flask with agitator, thermometer, prolong, loads onto tail gas absorption retrieving arrangement in reflux, is first separated SO in tail gas absorption retrieving arrangement under cryogenic condensation device
2, use NaOH alkaline solution; Less than 5 DEG C drip 18g sulfur oxychloride and constantly stir, adding DMF 5g, under catalyst action, drip off and be slowly heated to 85 DEG C, reflux 2 hours until react end after releasing without gas, obtained stearic acid chloride crude product; Be 730-840mmHg by thick for precipitation stearic acid chloride product in vacuum tightness, temperature is carry out distilation under the condition of 120-140 DEG C, by residual chloride sulfoxide and catalyst recovery, obtains stearic acid chloride.
Embodiment 2:
By 10g stearic acid, 0.10g water adds in the there-necked flask with agitator, thermometer, prolong, loads onto tail gas absorption retrieving arrangement in reflux, is first separated SO in tail gas absorption retrieving arrangement under cryogenic condensation device
2, use NaOH alkaline solution; Less than 3 DEG C drip 25g sulfur oxychloride and constantly stir, adding N,N-dimethylacetamide 8g, under catalyst action, drip off and be slowly heated to 90 DEG C, reflux 2 hours until react end after releasing without gas, obtained stearic acid chloride crude product; Be 730-840mmHg by thick for precipitation stearic acid chloride product in vacuum tightness, temperature is carry out distilation under the condition of 120-140 DEG C, by residual chloride sulfoxide and catalyst recovery, obtains stearic acid chloride.
Embodiment 3:
By 10g stearic acid, 0.10g water adds in the there-necked flask with agitator, thermometer, prolong, loads onto tail gas absorption retrieving arrangement in reflux, is first separated SO in tail gas absorption retrieving arrangement under cryogenic condensation device
2, use NaOH alkaline solution; Less than 0 DEG C drips 30g sulfur oxychloride and constantly stirs, adding triethylamine 10g, under catalyst action, drip off and be slowly heated to 95 DEG C, refluxes 2 hours until react end after releasing without gas, obtained stearic acid chloride crude product; Be 730-840mmHg by thick for precipitation stearic acid chloride product in vacuum tightness, temperature is carry out distilation under the condition of 120-140 DEG C, by residual chloride sulfoxide and catalyst recovery, obtains stearic acid chloride.
Embodiment 4:
By 10g stearic acid, 0.10g water adds in the there-necked flask with agitator, thermometer, prolong, loads onto tail gas absorption retrieving arrangement in reflux, is first separated SO in tail gas absorption retrieving arrangement under cryogenic condensation device
2, use NaOH alkaline solution; Less than 4 DEG C drip 22g sulfur oxychloride and constantly stir, adding pyridine 12g, under catalyst action, drip off and be slowly heated to 90 DEG C, reflux 2 hours until react end after releasing without gas, obtained stearic acid chloride crude product; Be 730-840mmHg by thick for precipitation stearic acid chloride product in vacuum tightness, temperature is carry out distilation under the condition of 120-140 DEG C, by residual chloride sulfoxide and catalyst recovery, obtains stearic acid chloride.
Claims (5)
1. a synthetic method for stearic acid chloride, is characterized in that, comprises the steps:
Step one: by stearic acid and water 100:1 mixing by weight, sulfur oxychloride is dripped under adding at 0-5 DEG C, dropping limit, limit is stirred, and drips after terminating, adds N, dinethylformamide makees catalyzer, be warming up to 85-95 DEG C of back flow reaction 2h, reaction end gas carries out vent gas treatment by exhaust gas processing device, and reaction terminates to releasing without gas, cooling, separates out the thick product of stearic acid chloride;
Step 2: be 730-840mmHg in vacuum tightness by thick for precipitation stearic acid chloride product, temperature is carry out distilation under the condition of 120-140 DEG C, by residual chloride sulfoxide and catalyst recovery, obtains stearic acid chloride.
2. the synthetic method of stearic acid chloride according to claim 1, is characterized in that, the mass ratio of described stearic acid and sulfur oxychloride is 1:1.8-3.
3. the synthetic method of stearic acid chloride according to claim 1, is characterized in that, the mass ratio of described stearic acid and catalyzer is 1:0.5-1.2%.
4. the synthetic method of stearic acid chloride according to claim 1, is characterized in that, described catalyzer is can also be any one in N,N-dimethylacetamide, triethylamine, pyridine, cetyl trimethylammonium bromide.
5. the synthetic method of stearic acid chloride according to claim 1, is characterized in that, in described step one, first vent gas treatment is separated SO in order under cryogenic condensation device
2, then absorb HCl gas by NaOH solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510705451.XA CN105254488A (en) | 2015-10-26 | 2015-10-26 | Synthesis method for stearoyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510705451.XA CN105254488A (en) | 2015-10-26 | 2015-10-26 | Synthesis method for stearoyl chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105254488A true CN105254488A (en) | 2016-01-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510705451.XA Pending CN105254488A (en) | 2015-10-26 | 2015-10-26 | Synthesis method for stearoyl chloride |
Country Status (1)
| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108951285A (en) * | 2018-08-02 | 2018-12-07 | 宁波高新区诠宝绶新材料科技有限公司 | A kind of preparation method of Neutral Papermaking polymeric material |
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|---|---|---|---|---|
| WO2001004080A1 (en) * | 1999-07-12 | 2001-01-18 | Hercules Incorporated | Process for obtaining acyl halide |
| US20080281113A1 (en) * | 2007-05-10 | 2008-11-13 | Multi Formulations Ltd | Preparation of amino acid-fatty acid anhydrides |
| CN101863753A (en) * | 2010-06-17 | 2010-10-20 | 东莞市广益食品添加剂实业有限公司 | Method for preparing palmitoyl chloride |
| CN102219714A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | N,N-dual fat acyl diamine diacetate dipolyoxyethylene ether bisulphonate and preparation method thereof |
| CN102218282A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Dual-carboxylate gemini surfactant resistant to high temperature and high salt and preparation method thereof |
| CN104877654A (en) * | 2015-05-08 | 2015-09-02 | 江南大学 | Compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof |
-
2015
- 2015-10-26 CN CN201510705451.XA patent/CN105254488A/en active Pending
Patent Citations (6)
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|---|---|---|---|---|
| WO2001004080A1 (en) * | 1999-07-12 | 2001-01-18 | Hercules Incorporated | Process for obtaining acyl halide |
| US20080281113A1 (en) * | 2007-05-10 | 2008-11-13 | Multi Formulations Ltd | Preparation of amino acid-fatty acid anhydrides |
| CN102219714A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | N,N-dual fat acyl diamine diacetate dipolyoxyethylene ether bisulphonate and preparation method thereof |
| CN102218282A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Dual-carboxylate gemini surfactant resistant to high temperature and high salt and preparation method thereof |
| CN101863753A (en) * | 2010-06-17 | 2010-10-20 | 东莞市广益食品添加剂实业有限公司 | Method for preparing palmitoyl chloride |
| CN104877654A (en) * | 2015-05-08 | 2015-09-02 | 江南大学 | Compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108951285A (en) * | 2018-08-02 | 2018-12-07 | 宁波高新区诠宝绶新材料科技有限公司 | A kind of preparation method of Neutral Papermaking polymeric material |
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Application publication date: 20160120 |
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