CN101045676A - Synthetic method of 1-chlorine-3-methoxy propane - Google Patents
Synthetic method of 1-chlorine-3-methoxy propane Download PDFInfo
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- CN101045676A CN101045676A CNA2006100500633A CN200610050063A CN101045676A CN 101045676 A CN101045676 A CN 101045676A CN A2006100500633 A CNA2006100500633 A CN A2006100500633A CN 200610050063 A CN200610050063 A CN 200610050063A CN 101045676 A CN101045676 A CN 101045676A
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- Prior art keywords
- chloro
- methoxypropane
- synthesizing
- bromochloropropane
- inert solvent
- Prior art date
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- 238000010189 synthetic method Methods 0.000 title 1
- BQLHMMQUVJCTAN-UHFFFAOYSA-N 1-chloro-3-methoxypropane Chemical compound COCCCCl BQLHMMQUVJCTAN-UHFFFAOYSA-N 0.000 claims abstract description 27
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 16
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012044 organic layer Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012442 inert solvent Substances 0.000 claims description 9
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- XINJSHLATKLNMN-UHFFFAOYSA-N sodium;benzene;methanolate Chemical compound [Na+].[O-]C.C1=CC=CC=C1 XINJSHLATKLNMN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- AQVWVFMAJAIJFG-UHFFFAOYSA-N 1-chloro-3-ethoxypropane Chemical compound CCOCCCCl AQVWVFMAJAIJFG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- -1 sodium methoxide cyclohexane Chemical compound 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for synthesizing 1-Cl-3-methoxy propane includes such steps as dripping the sodium methylate dispersed in inertial solvent into 1,3-bromochloropropane under existence of phase-transfer catalyst, reacting, filtering for removing sodium bromide, washing the filtered cake by inertial solvent, collecting organic layer, water washing until pH=5-7 to obtain coarse product, drying, filtering, and rectifying filtrate.
Description
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a preparation method of 1-chloro-3-methoxypropane.
Background
1-chloro-3-methoxypropane is an important intermediate of organic compounds, has wide application range, and can be researched as early as the beginning of the last century, such as (CA 3: 1173) Acad Sci Fennicae 3A, 1-103 and (CA 27: 16153) org. Synthesis 8, 112, Ann Chim 18303-94, 1932, to prepare Cl (CH) from 1, 3-propanediol3)3OH, then dimethyl sulfate methylThe methylation yield of the 1-chloro-3-methoxy propane is only 65 percent.
(CA 25: 3958) from HO (CH)3)3Starting from OMe, halogenating with phosphorus trihalide to prepare 1-chloro-3-methoxypropane, wherein the yield is only 58-76%; (CA 32: 41418) BER.71B, 574-5(1938) was prepared in 90% yield starting from 1, 3-propanediol.
(CA46：14431) J. org Chem 16, 704 to 7(1951) and (CA 52: 17320e) Compt rend246, 1868-7, etc. from HO (CH)3)3OMe starts with a method for increasing the yield of halogenated compounds.
Some of the above methods have low yields; some 1, 3-propylene glycol needs to be used as a raw material, production of the 1, 3-propylene glycol is not seen at home, and only Degussa, Shell and Dapont in Germany produce the 1, 3-propylene glycol, but imported reagents are distinguished and noble, high in production cost and difficult to obtain, and cannot meet the requirement of domestic large-scale industrial production.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide a novel synthesis method of 1-chloro-3-methoxypropane, so that the operation is simple, the yield is improved, and the production cost is reduced.
Therefore, the invention adopts the following technical scheme: the synthesis method of the 1-chloro-3-methoxy propane comprises the following steps: in the presence of a phase transfer catalyst, dropwise adding a dispersion of sodium methoxide in an inert solvent into 1, 3-bromochloropropane, carrying out heat preservation reaction after dropwise adding, filtering to remove sodium bromide after complete reaction, washing a filter cake with the inert solvent, combining organic layers, washing with water to obtain a 1-chloro-3-methoxypropane crude product, drying, filtering, and rectifying the filtrate. The invention uses cheap 1, 3-bromochloropropane (which is prepared by starting from propylene chloride and performing anti-Markov addition on hydrogen bromide, and is produced on a large scale in China) as a raw material, and the raw material is easy to prepare, has low cost, is simple and convenient to operate, and has high yield. The synthetic route is as follows:
when sodium methoxide in the invention is changed into sodium ethoxide, 1-chloro-3-ethoxypropane can be prepared by adopting the method of the invention.
According to the synthesis method of the 1-chloro-3-methoxy propane, the molar ratio of the 1, 3-bromochloropropane to the anhydrous sodium methoxide is 1: 0.9-1.2, the reaction can be quantitatively and completely mono-etherified, and the reaction yield is high.
In the synthesis method of the 1-chloro-3-methoxy propane, the volume ratio of the 1, 3-bromochloropropane to the inert solvent is 1: 3-10; the inert solvent is benzene, petroleum ether or cyclohexane, can obtain good effect, preferably benzene, and has the advantages of simplicity, easy obtaining, low price and easy rectification and separation with products.
In the method for synthesizing the 1-chloro-3-methoxypropane, the phase transfer catalyst is tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), benzyltriethylammonium chloride (TEAC) or benzyltrimethylammonium chloride (BTMAC), preferably benzyltrimethylammonium chloride (BTMAC), and the dosage of the phase transfer catalyst is 0.01-0.1 time of the weight of the 1, 3-bromochloropropane. The use of the phase transfer catalyst greatly shortens the reaction time, reduces the reaction temperature and obtains higher yield. If not, the reaction lasts for 24 hours, and the conversion rate is only about 45 percent.
According to the synthesis method of the 1-chloro-3-methoxy propane, the reaction temperature during dripping is 20-110 ℃, the heat preservation temperature is 50-80 ℃, the reaction temperature is low, the range is wide, and the reaction is easy to control.
The invention has the following advantages: the method has the advantages of easily obtained raw materials, mild reaction conditions, simple and convenient operation, high yield and low cost, and is very suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1 preparation of benzene Dispersion of anhydrous sodium methoxide
A500 ml three-neck flask is added with 300g (1.5mol) of 27% sodium methoxide methanol solution, the methanol is recovered under reduced pressure in magnetic stirring, nitrogen is introduced for protection, and 300ml of benzene is added to obtain anhydrous sodium methoxide benzene dispersion for later use, and other solvent dispersants are similar.
EXAMPLE 21 preparation of chloro-3-methoxypropane
Adding 300ml of sodium methoxide benzene dispersion into a dropping funnelwith a balance tube, adding 236.2g (1.5mol) of 1, 3-bromochloropropane and 6g of anhydrous tetrabutylammonium bromide (TBAB) into a 500ml four-neck flask with stirring slurry, a thermometer and nitrogen protection, heating by an oil bath to control the external temperature to be 80 ℃, finishing dropping within 5 hours, carrying out heat preservation reaction for 3 hours, sampling GC to detect that the reaction is finished completely, cooling, filtering to remove inorganic salt sodium bromide, washing with benzene, combining filtrate, washing a benzene layer for three times, measuring the pH of water to be 6-7, approaching neutrality, drying with anhydrous sodium sulfate, filtering, carrying out normal pressure rectification on the filtrate, and collecting 110-112 ℃ fractions to obtain 151g (the yield is 92.8%) of the target product 1-chloro-3-methoxypropane.
EXAMPLE 31 preparation of chloro-3-methoxypropane
Adding 300ml of anhydrous sodium methoxide petroleum ether dispersion into a dropping funnel with a balance tube, adding 220g (1.4mol) of 1, 3-bromochloropropane and 5g of anhydrous benzyl trimethyl ammonium chloride (BTMAC) into a 500ml four-neck flask with stirring slurry, a thermometer and nitrogen protection, heating in an oil bath to control the external temperature to be 60 ℃, finishing dropping within 2 hours, carrying out heat preservation reaction for 2 hours, sampling, detecting the reaction completion by a GC (gas chromatography), cooling, filtering to remove inorganic salt sodium bromide, washing with benzene, combining filtrate, washing a benzene layer for three times, measuring the pH of water to be 6-7, approaching neutrality, drying with anhydrous sodium sulfate, filtering, carrying out normal pressure rectification on the filtrate, and collecting 110-112 ℃ fractions to obtain 140g of the target product 1-chloro-3-methoxypropane (the yield is 92.2%).
EXAMPLE 41 preparation of chloro-3-methoxypropane
Adding 300ml of anhydrous sodium methoxide cyclohexane dispersion into a dropping funnel with a balance tube, adding 220g (1.4mol) of 1, 3-bromochloropropane and 3g of anhydrous benzyltriethylammonium chloride (TEACC) into a 500ml four-neck flask with stirring slurry, a thermometer and nitrogen protection, heating by an oil bath to control the external temperature to be 50 ℃, finishing dropping within 10 hours, carrying out heat preservation reaction for 1 hour, sampling GC to detect that the reaction is completely finished, cooling, filtering to remove inorganic salt sodium bromide, washing with benzene, combining filtrate, washing a benzene layer for three times, measuring the pH of water to be 6-7, approaching neutrality, drying with anhydrous sodium sulfate, filtering, carrying out normal pressure rectification on the filtrate, and collecting 110-112 ℃ fractions to obtain 139g (the yield is 91.5%) of the target product 1-chloro-3-methoxypropane.
The present invention is not limited to the above-described embodiment, which is an optimized embodiment.
Claims (7)
1. The synthesis method of the 1-chloro-3-methoxy propane comprises the following steps: in the presence of a phase transfer catalyst, dropwise adding a dispersion of sodium methoxide in an inert solvent into 1, 3-bromochloropropane, carrying out heat preservation reaction after dropwise adding, filtering to remove sodium bromide after complete reaction, washing a filter cake with the inert solvent, combining organic layers, washing with water until the pH value is 5-7 to obtain a 1-chloro-3-methoxypropane crude product, drying, filtering, and rectifying filtrate.
2. The method for synthesizing 1-chloro-3-methoxypropane as claimed in claim 1, wherein the molar ratio of 1, 3-bromochloropropane to sodium methoxide is 1: 0.9-1.2.
3. The method for synthesizing 1-chloro-3-methoxypropane as claimed in claim 1 or 2, wherein the volume ratio of 1, 3-bromochloropropane to inert solvent is 1: 3-10, and the inert solvent is benzene, petroleum ether or cyclohexane.
4. The method for synthesizing 1-chloro-3-methoxypropane as claimed in claim 3, wherein said inert solvent is benzene.
5. The method for synthesizing 1-chloro-3-methoxypropane as claimed in claim 3, wherein the phase transfer catalyst is tetrabutylammonium bromide, tetrabutylammonium chloride, benzyltriethylammonium chloride or benzyltrimethylammonium chloride, and the amount of the catalyst is 0.01 to 0.1% by weight of 1, 3-bromochloropropane.
6. The method of synthesizing 1-chloro-3-methoxypropane as claimed in claim 5, wherein the phase transfer catalyst is benzyltrimethylammonium chloride.
7. The method for synthesizing 1-chloro-3-methoxypropane as claimed in claim 5, wherein the reaction temperature at the time of dropping is from 20 ℃ to 110 ℃ and the holding temperature is from 50 ℃ to 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100500633A CN100526275C (en) | 2006-03-27 | 2006-03-27 | Synthetic method of 1-chlorine-3-methoxy propane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100500633A CN100526275C (en) | 2006-03-27 | 2006-03-27 | Synthetic method of 1-chlorine-3-methoxy propane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101045676A true CN101045676A (en) | 2007-10-03 |
| CN100526275C CN100526275C (en) | 2009-08-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2006100500633A Expired - Fee Related CN100526275C (en) | 2006-03-27 | 2006-03-27 | Synthetic method of 1-chlorine-3-methoxy propane |
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| CN (1) | CN100526275C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643172A (en) * | 2012-04-16 | 2012-08-22 | 阜新恒通氟化学有限公司 | Preparation method of perfluoro-alkylethylalkyl ether |
| CN113791149A (en) * | 2021-09-07 | 2021-12-14 | 石家庄四药有限公司 | Detection method of 1-chloro-3-methoxypropane related substances |
-
2006
- 2006-03-27 CN CNB2006100500633A patent/CN100526275C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643172A (en) * | 2012-04-16 | 2012-08-22 | 阜新恒通氟化学有限公司 | Preparation method of perfluoro-alkylethylalkyl ether |
| CN113791149A (en) * | 2021-09-07 | 2021-12-14 | 石家庄四药有限公司 | Detection method of 1-chloro-3-methoxypropane related substances |
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| Publication number | Publication date |
|---|---|
| CN100526275C (en) | 2009-08-12 |
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