CN111170818A - Clean production method of cyclopropane - Google Patents
Clean production method of cyclopropane Download PDFInfo
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- CN111170818A CN111170818A CN201910609628.4A CN201910609628A CN111170818A CN 111170818 A CN111170818 A CN 111170818A CN 201910609628 A CN201910609628 A CN 201910609628A CN 111170818 A CN111170818 A CN 111170818A
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- Prior art keywords
- cyclopropane
- intermediate product
- finished
- synthesis
- triphosgene
- Prior art date
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- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000013067 intermediate product Substances 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 24
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 24
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 13
- BLJCOTKCUHBCSK-UHFFFAOYSA-N acetylene;cyclopropane Chemical group C#C.C1CC1 BLJCOTKCUHBCSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 12
- HVCFCNAITDHQFX-UHFFFAOYSA-N 1-cyclopropylethanone Chemical compound CC(=O)C1CC1 HVCFCNAITDHQFX-UHFFFAOYSA-N 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000008096 xylene Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 10
- 238000003860 storage Methods 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009776 industrial production Methods 0.000 abstract description 7
- 238000009835 boiling Methods 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- DBOLUUOSJMQAKB-UHFFFAOYSA-N cyclopropane;propan-2-one Chemical compound C1CC1.CC(C)=O DBOLUUOSJMQAKB-UHFFFAOYSA-N 0.000 abstract 1
- NPTDXPDGUHAFKC-UHFFFAOYSA-N ethynylcyclopropane Chemical group C#CC1CC1 NPTDXPDGUHAFKC-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 4
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DEWLEGDTCGBNGU-UHFFFAOYSA-N 1,3-dichloropropan-2-ol Chemical compound ClCC(O)CCl DEWLEGDTCGBNGU-UHFFFAOYSA-N 0.000 description 1
- 229940124321 AIDS medicine Drugs 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- XPOQHMRABVBWPR-UHFFFAOYSA-N Efavirenz Natural products O1C(=O)NC2=CC=C(Cl)C=C2C1(C(F)(F)F)C#CC1CC1 XPOQHMRABVBWPR-UHFFFAOYSA-N 0.000 description 1
- -1 and currently Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- XPOQHMRABVBWPR-ZDUSSCGKSA-N efavirenz Chemical compound C([C@]1(C2=CC(Cl)=CC=C2NC(=O)O1)C(F)(F)F)#CC1CC1 XPOQHMRABVBWPR-ZDUSSCGKSA-N 0.000 description 1
- 229960003804 efavirenz Drugs 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000012840 feeding operation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/18—Preparation of halogenated hydrocarbons by replacement by halogens of oxygen atoms of carbonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a clean production method of cyclopropane, which comprises two steps of synthesis of monochlorene intermediate product and synthesis of cyclopropane, wherein the monochlorene intermediate product is synthesized by adding triphosgene into cyclopropane methyl ketone, and the monochlorene intermediate product is synthesized by adding potassium hydroxide to obtain the finished product of the cyclopropane. The clean production method of the cyclopropane acetylene provided by the invention adopts triphosgene to chlorinate, and then eliminates the triphosgene to obtain the cyclopropane acetylene, the process route is short, the three wastes are few, the triphosgene has strong stability, a small amount of decomposition is carried out at the boiling point, the cyclopropane acetylene is decomposed into hydrogen chloride and carbon dioxide after the reaction is finished, no waste liquid is generated, no harsh conditions exist in storage, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a clean production method of cyclopropargyne.
Background
The cyclopropyl acetylene is an important intermediate of an anti-AIDS drug efavirenz, and currently, cyclopropyl methyl ketone is mainly used as a raw material in industrial production, and two main ways exist: 1. chloridizing with phosphorus pentachloride to obtain dichloride, eliminating the dichloride with triethylamine to obtain monochlorene, and eliminating with potassium hydroxide to obtain cyclopropylacetylene; 2. the dichloro product is directly subjected to potassium hydroxide elimination to obtain the cyclopropane. By adopting the process, phosphorus pentachloride can be used, a special warehouse is required for storing the phosphorus pentachloride, water contact is strictly forbidden, the storage requirement is high, hydrochloric acid smoke exists in a feeding place for a long time due to moisture in the air during feeding, the use amount is large, and great trouble is brought to feeding operation; after chlorination is finished, phosphorus oxychloride as a byproduct can be produced, and the storage requirement of the phosphorus oxychloride is basically consistent with that of phosphorus pentachloride, so that great safety risk is brought to storage of enterprises.
And the dichlorohydrin is unstable and cannot be stored for a long time, particularly water is avoided, high requirements are provided for equipment, raw materials and operation of the reaction in the step, the reaction yield in the step is low, and the industrial production is not facilitated.
Disclosure of Invention
The invention aims to provide a clean production method of cyclopropane, which adopts triphosgene to chlorinate and then eliminates to obtain the cyclopropane, has short process route, less three wastes and strong stability of the triphosgene, has little decomposition at the boiling point, decomposes into hydrogen chloride and carbon dioxide after the reaction is finished, does not generate waste liquid, has no harsh storage condition, is suitable for industrial production and solves the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a clean production method of cycloproplyacetylene comprises two steps of synthesis of monochloroethylene intermediate product and synthesis of cycloproplyacetylene, wherein the monochloroethylene intermediate product is synthesized by adding triphosgene into cyclopropylmethyl ketone, and the monochloroethylene intermediate product is synthesized by adding potassium hydroxide to obtain the cycloproplyacetylene finished product.
Preferably, the synthesis of the monochloroalkene intermediate comprises the following steps:
step 1: adding 1200ml of xylene into a clean 3000ml reaction bottle, and adding 470-570 g of triphosgene;
step 2: dripping 392-480 g of cyclopropyl methyl ketone at 15-65 ℃, preserving heat for 2-5 h at the temperature after dripping, heating to 120-170 ℃ after preserving heat, preserving heat for 8h, and finishing preserving heat;
and step 3: distilling and recovering 130-180 ℃ fractions under normal pressure, and distilling under reduced pressure until the fractions are not distilled;
and 4, step 4: and after distillation, rectifying the distillate to obtain 670-700 g of monochlorene intermediate product, and recycling the xylene for reuse.
Preferably, the synthesis of cyclopropylacetylene comprises the following steps:
step 1: adding 1170-1430 kg of DMSO and 432-528 kg of potassium hydroxide into a 3000ml clean reaction bottle, and after the addition is finished, heating to 100-160 ℃;
step 2: dripping the monochlorene intermediate, collecting fraction with gas phase temperature of 50-105 ℃ in the dripping process, continuing distilling and collecting fraction after dripping is finished, and stopping distilling until no fraction flows out at the temperature;
and step 3: and rectifying the distilled fraction to obtain 200-208 g of a finished cyclopropane acetylene product.
Compared with the prior art, the invention has the beneficial effects that: the clean production method of the cyclopropane acetylene provided by the invention adopts triphosgene to chlorinate, and then eliminates to obtain the cyclopropane acetylene, the process route is short, the three wastes are few, the triphosgene has strong stability, a small amount of decomposition is carried out at the boiling point, the reaction is decomposed into hydrogen chloride and carbon dioxide after the reaction is finished, no waste liquid is generated, the storage is not under harsh conditions, the method is suitable for industrial production, the reaction of dichlorine is reduced, the operability is greatly improved, and the product yield is improved.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of cyclopropylacetylene according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, a clean production method of cyclopropylacetylene includes two steps of synthesis of a monochlorene intermediate product and synthesis of cyclopropylacetylene, wherein a monochlorene intermediate product is synthesized by adding triphosgene to cyclopropylmethyl ketone, and a cyclopropylacetylene finished product is synthesized by adding potassium hydroxide to the monochlorene intermediate product.
Wherein, the synthesis of the monochlorene intermediate product comprises the following steps: 1200ml of xylene is added into a clean 3000ml reaction bottle, and 470g of triphosgene is added; adding 436g of cyclopropyl methyl ketone dropwise at 15 ℃, preserving heat for 2h at the temperature after the addition is finished, and then heating to 120 ℃ for preserving heat for 8h after the heat preservation is finished, wherein the heat preservation is finished; distilling and recovering 130 ℃ fraction under normal pressure, and distilling under reduced pressure after the fraction is not distilled; after distillation, the distillate is rectified to obtain 670g of monochlorene intermediate product, and the xylene is recovered and reused.
The synthesis of the cyclopropane comprises the following steps: adding DMSO1170kg and 480kg of potassium hydroxide into a 3000ml clean reaction bottle, and heating to 100 ℃ after the addition is finished; dripping the monochlorene intermediate, collecting fraction with gas phase temperature of 50 ℃ in the dripping process, continuing to distill and collect fraction after finishing dripping until no fraction flows out at the temperature; the distilled fraction is rectified to obtain 200g of a finished product of the cyclopropane.
Example 2
A clean production method of cycloproplyacetylene comprises two steps of synthesis of monochloroethylene intermediate product and synthesis of cycloproplyacetylene, wherein the monochloroethylene intermediate product is synthesized by adding triphosgene into cyclopropylmethyl ketone, and the monochloroethylene intermediate product is synthesized by adding potassium hydroxide to obtain the cycloproplyacetylene finished product.
Wherein, the synthesis of the monochlorene intermediate product comprises the following steps: 1200ml of xylene is added into a clean 3000ml reaction bottle, and 520g of triphosgene is added; dripping 392g of cyclopropyl methyl ketone at 45 ℃, preserving heat for 3 hours at the temperature after dripping is finished, and then heating to 140 ℃ for preserving heat for 8 hours after heat preservation is finished, wherein the heat preservation is finished; distilling under normal pressure to recover 150 deg.C fraction, and distilling under reduced pressure; after distillation, the distillate is rectified to obtain 680g monochlorene intermediate product, and the xylene is recovered and reused.
The synthesis of the cyclopropane comprises the following steps: adding DMSO1300kg and potassium hydroxide 432kg into a 3000ml clean reaction bottle, and heating to 130 ℃ after the addition is finished; dripping the monochlorene intermediate, collecting the fraction with the gas phase temperature of 80 ℃ in the dripping process, continuing to distill and collect the fraction after the dripping is finished until no fraction flows out at the temperature; 204g of cyclopropyl acetylene finished product is obtained after distillation and rectification of the distillate.
Example 3
A clean production method of cycloproplyacetylene comprises two steps of synthesis of monochloroethylene intermediate product and synthesis of cycloproplyacetylene, wherein the monochloroethylene intermediate product is synthesized by adding triphosgene into cyclopropylmethyl ketone, and the monochloroethylene intermediate product is synthesized by adding potassium hydroxide to obtain the cycloproplyacetylene finished product.
Wherein, the synthesis of the monochlorene intermediate product comprises the following steps: 1200ml of xylene is added into a clean 3000ml reaction bottle, and 570g of triphosgene is added; 480g of cyclopropyl methyl ketone is dripped at 65 ℃, after the dripping is finished, the temperature is kept for 5h, and after the temperature is kept, the temperature is raised to 170 ℃ again, the temperature is kept for 8h, and the temperature is kept; distilling under normal pressure to recover 180 deg.C fraction, and distilling under reduced pressure; after distillation, the distillate is rectified to obtain 700g of monochlorene intermediate product, and the xylene is recovered and reused.
The synthesis of the cyclopropane comprises the following steps: adding DMSO1430kg and 528kg of potassium hydroxide into a 3000ml clean reaction bottle, and heating to 160 ℃ after the addition is finished; dripping the monochlorene intermediate, collecting the fraction with the gas phase temperature of 105 ℃ in the dripping process, continuing to distill and collect the fraction after finishing dripping until no fraction flows out at the temperature; and distilling the distillate to obtain 208g of cyclopropyl acetylene finished products after rectification.
Compared with the existing synthesis process, the method for preparing the cyclopropanevinylene has the advantages that triphosgene is adopted for chlorination, and then the cyclopropanevinylene is eliminated, so that the process route is short, the three wastes are few, the triphosgene has strong stability, a small amount of decomposition is carried out at the boiling point, the cyclopropanevinylene is decomposed into hydrogen chloride and carbon dioxide after the reaction is finished, no waste liquid is generated, no harsh condition exists in storage, and the method is suitable for industrial production.
In conclusion, the clean production method of the cyclopropane acetylene provided by the invention adopts triphosgene to chlorinate, and then eliminates the triphosgene to obtain the cyclopropane acetylene, the process route is short, the three wastes are less, the triphosgene has strong stability, a small amount of decomposition is carried out at the boiling point, the triphosgene is decomposed into hydrogen chloride and carbon dioxide after the reaction is finished, no waste liquid is generated, no harsh condition exists in storage, and the method is suitable for industrial production.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (3)
1. A clean production method of cycloproplyacetylene is characterized by comprising two steps of synthesis of monochloroethylene intermediate product and synthesis of cycloproplyacetylene, wherein the monochloroethylene intermediate product is synthesized by adding triphosgene into cyclopropylmethyl ketone, and the monochloroethylene intermediate product is synthesized by adding potassium hydroxide to obtain the cycloproplyacetylene finished product.
2. A clean production method of cyclopropane according to claim 1, which is characterized in that the synthesis of monochlorene intermediate product comprises the following steps:
step 1: adding 1200ml of xylene into a clean 3000ml reaction bottle, and adding 470-570 g of triphosgene;
step 2: dripping 392-480 g of cyclopropyl methyl ketone at 15-65 ℃, preserving heat for 2-5 h at the temperature after dripping, heating to 120-170 ℃ after preserving heat, preserving heat for 8h, and finishing preserving heat;
and step 3: distilling and recovering 130-180 ℃ fractions under normal pressure, and distilling under reduced pressure until the fractions are not distilled;
and 4, step 4: and after distillation, rectifying the distillate to obtain 670-700 g of monochlorene intermediate product, and recycling the xylene for reuse.
3. The clean production method of cyclopropane according to claim 1, which is characterized in that the synthesis of cyclopropane comprises the following steps:
step 1: adding 1170-1430 kg of DMSO and 432-528 kg of potassium hydroxide into a 3000ml clean reaction bottle, and after the addition is finished, heating to 100-160 ℃;
step 2: dripping the monochlorene intermediate, collecting fraction with gas phase temperature of 50-105 ℃ in the dripping process, continuing distilling and collecting fraction after dripping is finished, and stopping distilling until no fraction flows out at the temperature;
and step 3: and rectifying the distilled fraction to obtain 200-208 g of a finished cyclopropane acetylene product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910609628.4A CN111170818A (en) | 2019-07-08 | 2019-07-08 | Clean production method of cyclopropane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910609628.4A CN111170818A (en) | 2019-07-08 | 2019-07-08 | Clean production method of cyclopropane |
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| CN201910609628.4A Pending CN111170818A (en) | 2019-07-08 | 2019-07-08 | Clean production method of cyclopropane |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207864B1 (en) * | 1997-03-07 | 2001-03-27 | Basf Aktiengesellschaft | Process for preparing cyclopropylacetylene |
| CN102381925A (en) * | 2011-08-01 | 2012-03-21 | 海门瑞一医药科技有限公司 | Preparation method of cyclopropyl acetylene |
| CN105985223A (en) * | 2014-12-30 | 2016-10-05 | 安徽贝克联合制药有限公司 | Preparation method for cyclopropyl acetylene |
-
2019
- 2019-07-08 CN CN201910609628.4A patent/CN111170818A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207864B1 (en) * | 1997-03-07 | 2001-03-27 | Basf Aktiengesellschaft | Process for preparing cyclopropylacetylene |
| CN102381925A (en) * | 2011-08-01 | 2012-03-21 | 海门瑞一医药科技有限公司 | Preparation method of cyclopropyl acetylene |
| CN105985223A (en) * | 2014-12-30 | 2016-10-05 | 安徽贝克联合制药有限公司 | Preparation method for cyclopropyl acetylene |
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