CN102942470A - Production technology of pharmaceutical grade valeryl chloride - Google Patents
Production technology of pharmaceutical grade valeryl chloride Download PDFInfo
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- CN102942470A CN102942470A CN2012104320796A CN201210432079A CN102942470A CN 102942470 A CN102942470 A CN 102942470A CN 2012104320796 A CN2012104320796 A CN 2012104320796A CN 201210432079 A CN201210432079 A CN 201210432079A CN 102942470 A CN102942470 A CN 102942470A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 title abstract description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 37
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 claims abstract description 12
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 9
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 6
- -1 for example Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims 4
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 claims 3
- 239000003039 volatile agent Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003381 stabilizer Substances 0.000 abstract description 7
- 125000002252 acyl group Chemical group 0.000 abstract description 2
- 238000012824 chemical production Methods 0.000 abstract description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- STMIIPIFODONDC-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(O)(CCCC)CN1C=NC=N1 STMIIPIFODONDC-UHFFFAOYSA-N 0.000 description 1
- 239000004072 C09CA03 - Valsartan Substances 0.000 description 1
- GVGLGOZIDCSQPN-PVHGPHFFSA-N Heroin Chemical compound O([C@H]1[C@H](C=C[C@H]23)OC(C)=O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4OC(C)=O GVGLGOZIDCSQPN-PVHGPHFFSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002220 antihypertensive agent Substances 0.000 description 1
- 229940127088 antihypertensive drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IPVQLZZIHOAWMC-QXKUPLGCSA-N perindopril Chemical compound C1CCC[C@H]2C[C@@H](C(O)=O)N(C(=O)[C@H](C)N[C@@H](CCC)C(=O)OCC)[C@H]21 IPVQLZZIHOAWMC-QXKUPLGCSA-N 0.000 description 1
- 229960002582 perindopril Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- SJSNUMAYCRRIOM-QFIPXVFZSA-N valsartan Chemical compound C1=CC(CN(C(=O)CCCC)[C@@H](C(C)C)C(O)=O)=CC=C1C1=CC=CC=C1C1=NN=N[N]1 SJSNUMAYCRRIOM-QFIPXVFZSA-N 0.000 description 1
- 229960004699 valsartan Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了医药级正戊酰氯的生产工艺，涉及化工生产领域，将正戊酸、氯化亚砜分别由储罐经计量泵打入搪瓷反应釜中，n(正戊酸)∶n(氯化亚砜)=1.0∶1.2～1.0∶1.5，再以正戊酸计加入质量计1～5w‰的DMF，升温至50～90℃，直至反应至无气体放出；将上述氯化反应液真空吸入精馏釜中，以正戊酸计加入质量计1～5‰稳定剂，减压精馏，控制精馏釜温≤90℃，前馏分氯化亚砜收集至接收储罐，正戊酰氯收集至成品储罐。本发明通过添加富电子结构的稳定剂，使得酰基正离子优先与稳定剂结合，避免正戊酸酐的生成。同时降低精馏釜温度，降低正戊酰氯离解的平衡常数，提高精馏分离的稳定性。The invention discloses a production process of pharmaceutical-grade n-valeryl chloride, which relates to the field of chemical production. The n-valeric acid and the thionyl chloride are injected into an enamel reaction kettle through a metering pump from a storage tank respectively, n(n-valeric acid):n( Thionyl chloride)=1.0:1.2～1.0:1.5, then add DMF with a mass of 1～5w‰ in terms of n-valeric acid, and heat up to 50～90°C until no gas is released; the above-mentioned chlorination reaction solution Vacuum suction into the rectification kettle, add 1-5‰ stabilizer by mass in terms of n-valeric acid, rectify under reduced pressure, control the temperature of the rectification kettle to ≤90°C, collect the front fraction thionyl chloride into the receiving storage tank, Acyl chlorides are collected in product storage tanks. In the present invention, by adding a stabilizer with an electron-rich structure, the acyl positive ion is preferentially combined with the stabilizer to avoid the generation of n-valeric anhydride. At the same time, the temperature of the rectification kettle is lowered, the equilibrium constant of n-valeryl chloride dissociation is lowered, and the stability of rectification separation is improved.
Description
技术领域 technical field
本发明涉及化工生产领域，具体涉及一种医药级正戊酰氯的生产工艺。 The invention relates to the field of chemical production, in particular to a production process of pharmaceutical grade n-valeryl chloride.
背景技术 Background technique
正戊酰氯是一种具有广泛用途的化工产品，如可用于合成农药杀菌剂己唑醇；向列型苯基环己烷液晶材料；降压药培哚普利、缬沙坦、厄贝沙坦；以及用于有机合成领域的基团保护等。其中医药级正戊酰氯的产品附价值高，质量指标也最为严格，要求正戊酰氯含量≥99.5%、正戊酸酐含量≤0.2%、正戊酸含量≤0.25%、无磷元素残余等。 N-valeryl chloride is a chemical product with a wide range of uses, such as the synthesis of pesticide fungicide hexaconazole; nematic phenylcyclohexane liquid crystal material; antihypertensive drugs perindopril, valsartan, irbeza Tan; and group protection in the field of organic synthesis, etc. Among them, pharmaceutical-grade n-valeryl chloride has high added value and the most stringent quality indicators, requiring n-valeryl chloride content ≥ 99.5%, n-valeric anhydride content ≤ 0.2%, n-valeric acid content ≤ 0.25%, and no phosphorus residues.
正戊酰氯的生产方法是以正戊酸为原料，经氯化试剂氯化合成，可选的氯化试剂有光气、氯化亚砜、三氯化磷、五氯化磷，草酰氯等。从原料来源及成本考虑，氯化亚砜及三氯化磷的应用最为广泛。由于医药级正戊酰氯要求无磷元素残余，而三氯化磷氯化过程中生成的磷酸与戊酰氯沸点接近，后处理困难，故氯化亚砜为氯化试剂较为合适。 The production method of n-valeryl chloride is to use n-valeric acid as the raw material and synthesize it by chlorination with chlorinating reagents. The optional chlorinating reagents include phosgene, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, etc. . Considering the sources of raw materials and cost, thionyl chloride and phosphorus trichloride are the most widely used. Since the pharmaceutical grade n-valeryl chloride requires no residual phosphorus element, and the phosphoric acid generated during the chlorination process of phosphorus trichloride has a boiling point close to that of valeryl chloride, so post-treatment is difficult, so thionyl chloride is more suitable as a chlorination reagent.
氯化生产过程中通常添加DMF为催化剂，以提高反应动力学及氯化选择性，避免生成的正戊酰氯与未反应的正戊酸缩合形成正戊酸酐。其催化机理为：DMF与氯化亚砜经缩合、重排，脱去SO2形成Vilsmeier试剂，其氯化活性比氯化亚砜更强，使得羧酸优先与其发生氯化反应，机理如下所示。 In the chlorination production process, DMF is usually added as a catalyst to improve the reaction kinetics and chlorination selectivity, and avoid the condensation of n-valeryl chloride and unreacted n-valeric acid to form n-valeric anhydride. The catalytic mechanism is as follows: DMF and thionyl chloride undergo condensation and rearrangement to remove SO 2 to form Vilsmeier reagent. Its chlorination activity is stronger than that of thionyl chloride, so that carboxylic acid is preferentially chlorinated with it. The mechanism is as follows Show.
然而，该体系精馏收集的126-127℃馏分，纯度≥98%(GC)，其中正戊酸酐含量在1%左右，仅满足农药级产品指标，且精馏釜底残余5~10%黑色焦油。 However, the 126-127°C fraction collected by rectification in this system has a purity of ≥98% (GC), and the content of n-valeric anhydride is about 1%, which only meets the pesticide-grade product index, and 5-10% of the black residue at the bottom of the rectification tank tar.
发明内容 Contents of the invention
针对上述生产存在问题，本发明的目的在于提供一种高含量医药级正戊酰氯的生产工艺，本发明可通过以下技术方案实施： For above-mentioned production existence problem, the object of the present invention is to provide a kind of production technique of high-content pharmaceutical grade n-valeryl chloride, the present invention can be implemented through the following technical solutions:
1. 将正戊酸、氯化亚砜分别由储罐经计量泵打入搪瓷反应釜中，n(正戊酸):n(氯化亚砜)=1.0:1.2~1.0:1.5，再以正戊酸计加入1~5wt‰DMF，升温至50~90℃，直至反应至无气体放出； 1. Put n-valeric acid and thionyl chloride into the enamel reaction kettle through the metering pump respectively from the storage tank, n(n-valeric acid):n(thionyl chloride)=1.0:1.2~1.0:1.5, and then Add 1~5wt‰DMF to the meter of n-valeric acid, raise the temperature to 50~90℃, until no gas is released during the reaction;
2. 将上述氯化反应液真空吸入精馏釜中，以正戊酸计加入1~5wt‰稳定剂，减压精馏，控制精馏釜温≤90℃，前馏分氯化亚砜收集至接收储罐，正戊酰氯收集至成品储罐。 2. Vacuum suck the above-mentioned chlorination reaction liquid into the rectification kettle, add 1~5wt‰ stabilizer in terms of n-valeric acid, rectify under reduced pressure, control the temperature of the rectification kettle to ≤90°C, and collect the thionyl chloride in the front fraction Receiving storage tank, n-valeryl chloride is collected to the finished product storage tank.
其中步骤（2）所述的稳定剂结构见下式： Wherein the stabilizer structure described in step (2) sees the following formula:
其中R1、R2、R3均为富电子取代基，例如，苯基，烷基或烷氧基中的一种或几种。 Wherein R 1 , R 2 and R 3 are all electron-rich substituents, for example, one or more of phenyl, alkyl or alkoxy.
本发明的有益效果Beneficial effects of the present invention
一般精馏工序后期即使保持较高的回流比等，出料馏分中正戊酸酐含量逐步升高。由此可见，戊酰氯(125~127℃)与戊酸酐(228~230℃)沸点虽然相差较大，但存在共沸现象。其中正戊酸酐的可能生成机理如下所示。 Generally, even if a high reflux ratio is maintained in the later stage of the rectification process, the content of n-valeric anhydride in the output fraction will gradually increase. It can be seen that although the boiling points of valeryl chloride (125~127°C) and valeric anhydride (228~230°C) are quite different, there is an azeotropic phenomenon. The possible formation mechanism of n-valeric anhydride is shown below.
正戊酰氯受热后分子运动加剧，离解成酰基正离子与氯负离子。酰基正离子亲电进攻正戊酰氯的烯醇式互变异构体，形成酯类化合物，释放一分子氯化氢。该酯类化合物再次受到酰基正离子的亲电进攻，形成正戊酸酐和氯代烯烃。该机理符合生产过程中有氯化氢气体溢出及黑色焦油生成的现象。 The molecular motion of n-valeryl chloride intensifies after being heated, and dissociates into acyl cations and chloride anions. The acyl cation electrophilically attacks the enol tautomer of n-pentanoyl chloride to form an ester compound, releasing a molecule of hydrogen chloride. The ester compound is subjected to the electrophilic attack of the acyl cation again to form n-valeric anhydride and chlorinated alkenes. This mechanism is consistent with the phenomenon that hydrogen chloride gas overflows and black tar is generated during the production process.
本发明通过添加富电子结构的稳定剂，使得酰基正离子优先与稳定剂结合，避免正戊酸酐的生成。同时降低精馏釜温度，降低正戊酰氯离解的平衡常数，提高精馏分离的稳定性。 In the present invention, by adding a stabilizer with an electron-rich structure, the acyl positive ion is preferentially combined with the stabilizer to avoid the generation of n-valeric anhydride. At the same time, the temperature of the rectification kettle is lowered, the equilibrium constant of n-valeryl chloride dissociation is lowered, and the stability of rectification separation is improved.
具体实施例 specific embodiment
实施例1Example 1
将100kg正戊酸、140kg氯化亚砜分别由储罐，经计量泵打入500L搪瓷反应釜中，再加入0.1kg DMF，打开蒸汽阀门，升温至50℃，生成的酸性气体由尾气吸收装置进行吸收，反应直至无气体放出。将上述反应液真空吸入200L精馏釜中，加入0.1kg N,N-二甲基苯胺，减压精馏，控制釜温≤90℃，回收氯化亚砜23kg，收集正戊酰氯115kg，纯度99.7%(GC)，收率98%。 Put 100kg of n-valeric acid and 140kg of thionyl chloride into the 500L enamel reaction kettle through the metering pump respectively from the storage tank, then add 0.1kg of DMF, open the steam valve, and raise the temperature to 50°C, the generated acid gas is discharged from the tail gas absorption device Absorb and react until no gas is released. Vacuum suck the above reaction solution into a 200L rectification kettle, add 0.1kg of N,N-dimethylaniline, rectify under reduced pressure, control the temperature of the kettle to ≤90°C, recover 23kg of thionyl chloride, and collect 115kg of n-valeryl chloride. 99.7% (GC), yield 98%.
实施例2Example 2
将100kg正戊酸、175kg氯化亚砜分别由储罐，经计量泵打入500L搪瓷反应釜中，再加入0.2kg DMF，打开蒸汽阀门，升温至70℃，生成的酸性气体去尾气吸收装置进行吸收，反应直至无气体放出。将上述反应液真空吸入200L精馏釜中，加入0.5kg 三苯胺，减压精馏，控制釜温≤90℃，回收氯化亚砜57kg，收集正戊酰氯113kg，纯度99.6%(GC)，收率96%。 Put 100kg of n-valeric acid and 175kg of thionyl chloride into the 500L enamel reaction kettle through the metering pump respectively from the storage tank, then add 0.2kg of DMF, open the steam valve, raise the temperature to 70°C, and remove the generated acid gas to the tail gas absorption device Absorb and react until no gas is released. Vacuum the above reaction solution into a 200L rectification kettle, add 0.5kg of triphenylamine, rectify under reduced pressure, control the temperature of the kettle to ≤90°C, recover 57kg of thionyl chloride, collect 113kg of n-valeryl chloride, with a purity of 99.6% (GC), The yield is 96%.
实施例3Example 3
将100kg正戊酸、152kg氯化亚砜分别由储罐，经计量泵打入500L搪瓷反应釜中，再加入0.5kg DMF，打开蒸汽阀门，升温至90℃，生成的酸性气体去尾气吸收装置进行吸收，反应直至无气体放出。将上述反应液真空吸入200L精馏釜中，加入0.3kg 三乙醇胺，减压精馏，控制釜温≤90℃，回收氯化亚砜35kg，收集正戊酰氯114kg，纯度99.7%(GC)，收率97%。 Put 100kg of n-valeric acid and 152kg of thionyl chloride into the 500L enamel reaction kettle through the metering pump respectively from the storage tank, then add 0.5kg of DMF, open the steam valve, raise the temperature to 90°C, and remove the generated acid gas to the tail gas absorption device Absorb and react until no gas is released. Vacuum the above reaction solution into a 200L rectification kettle, add 0.3kg of triethanolamine, rectify under reduced pressure, control the temperature of the kettle to ≤90°C, recover 35kg of thionyl chloride, and collect 114kg of n-valeryl chloride with a purity of 99.7% (GC). The yield is 97%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880646A (en) * | 2014-03-13 | 2014-06-25 | 东力（南通）化工有限公司 | Hydrolysis-resistant rectifying process of isovaleryl chloride |
| CN115477578A (en) * | 2022-10-18 | 2022-12-16 | 中国人民解放军61699部队 | Purification method of nonanoyl chloride |
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| CN1373742A (en) * | 1999-09-13 | 2002-10-09 | 巴斯福股份公司 | Method for producing acid chlorides |
| CN101007774A (en) * | 2007-01-29 | 2007-08-01 | 浙江大学 | Method for synthesizing D-norvaline using n-pentanoic acid |
| US20100099911A1 (en) * | 2007-03-01 | 2010-04-22 | Mitsui Chemicals, Inc | Method for producing carboxylic acid chloride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880646A (en) * | 2014-03-13 | 2014-06-25 | 东力（南通）化工有限公司 | Hydrolysis-resistant rectifying process of isovaleryl chloride |
| CN115477578A (en) * | 2022-10-18 | 2022-12-16 | 中国人民解放军61699部队 | Purification method of nonanoyl chloride |
| CN115477578B (en) * | 2022-10-18 | 2024-04-26 | 中国人民解放军61699部队 | Purification method of nonanoyl chloride |
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