CN1044899C - 2.4－二氯氟苯制备方法 - Google Patents
2.4－二氯氟苯制备方法 Download PDFInfo
- Publication number
- CN1044899C CN1044899C CN94120005A CN94120005A CN1044899C CN 1044899 C CN1044899 C CN 1044899C CN 94120005 A CN94120005 A CN 94120005A CN 94120005 A CN94120005 A CN 94120005A CN 1044899 C CN1044899 C CN 1044899C
- Authority
- CN
- China
- Prior art keywords
- chloro
- gets
- dichlor fluorbenzene
- dichlorobenzene
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 6
- 238000006396 nitration reaction Methods 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- DPHCXXYPSYMICK-UHFFFAOYSA-N 2-chloro-1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(Cl)=C1 DPHCXXYPSYMICK-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- CMVQZRLQEOAYSW-UHFFFAOYSA-N 1,2-dichloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1Cl CMVQZRLQEOAYSW-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 238000001256 steam distillation Methods 0.000 claims description 3
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004334 fluoridation Methods 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- KQOOFMWRLDRDAX-UHFFFAOYSA-N 2-chloro-4-fluoro-1-nitrobenzene Chemical class [O-][N+](=O)C1=CC=C(F)C=C1Cl KQOOFMWRLDRDAX-UHFFFAOYSA-N 0.000 claims 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 229940117389 dichlorobenzene Drugs 0.000 abstract description 6
- 239000002360 explosive Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical class FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000003682 fluorination reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- -1 dinitro compound Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 2
- YSEMCVGMNUUNRK-UHFFFAOYSA-N 3-chloro-4-fluoroaniline Chemical compound NC1=CC=C(F)C(Cl)=C1 YSEMCVGMNUUNRK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- AIEXAPGVQZQOKH-UHFFFAOYSA-N ClC1=C(C=CC=C1)[N+](=O)[O-].[F] Chemical compound ClC1=C(C=CC=C1)[N+](=O)[O-].[F] AIEXAPGVQZQOKH-UHFFFAOYSA-N 0.000 description 1
- 241001101720 Murgantia histrionica Species 0.000 description 1
- 238000000297 Sandmeyer reaction Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/02—Monocyclic aromatic halogenated hydrocarbons
- C07C25/13—Monocyclic aromatic halogenated hydrocarbons containing fluorine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种2.4-二氯氟苯制备方法。本发明是从邻-二氯苯或对-二氯苯或两者的混合物出发经过硝化，氟化，氯化三次反应合成2.4-二氯氟苯。本发明克服了易爆炸的缺点，2.4-二氯氟苯中没有二氯氟苯的异构体，方法步骤比由氟氯苯胺为原料合成2.4-二氯氟苯要简便得多，采用对-二氯苯为原料或混合二氯苯为原料，原料成本降低，对-二氯苯硝化反应时几乎无副产品。
Description
本发明涉及2.4-二氯氟苯制备方法。
从前合成2.4-二氯氟苯的方法有以下几种：由2.4二硝基氟苯氯化制取，或由氟苯氯化制取，或者由3-氯-4-氟苯氨经重氮化，及Sandmeyer反应制取。
特开平-1-226836为利用2.4-二硝基氟苯(2.4-DNFB)在300℃以上与氯在反应管中反应合成2.4-二氯氟苯，这种方法缺点是二硝基化合物容易爆炸。
由氟苯制取2.4-二氯氟苯，氯化的结果，至少有六种异构体，特开平-4-1144采用这种方法，2.4-二氯氟苯生成率50～60％，选择性80％左右。异构体的分离十分困难。
由3-氯-4-氟苯氨(3-Cl-4-FBA)合成2.4-二氯氟苯方法路线太长，而且3-Cl-4-FBA的重氮化合物在Sandmeyer反应时易爆炸。
本发明的目的是提供一和2.4-二氯氟苯制备方法。
为了达到上述目的本发明采取下列措施：
2.4二氯氟苯制备方法为：
第一步浓硝酸65～70g，浓硫酸70～80g，在恒温条件下，升温至45～55℃，边搅拌边加入邻二氯苯75g，硝化反应结束后，分离废酸，用液碱中和，再水洗至中性，脱水干燥后得3.4～二氯硝基苯；
第二步，96g3.4～二氯硝基苯加140～150ml二甲基亚砜，搅拌溶解，缓慢加入氟化钾60g，氟化反应后，用水汽蒸馏得3-氯-4-氟硝基苯粗品，再经真空精馏得3-氯-4氟硝基苯纯品；
第三步，100g汽化的3-氯-4-氟硝基苯与氯气一起通入管式反应器，反应温度为380～400℃.氯化反应结束后得2.4-二氯氟苯粗品，再经真空脱除氯和二氧化氮，然后，精馏提纯得含量大于98％的2.4-二氯氟苯。
本发明的优点：
本发明克服了易爆炸的缺点；2.4-二氯氟苯中没有二氯氟苯的异构体；方法步骤比由氟氯苯胺为原料制取2.4-二氯氟苯要简便得多，采用对-二氯苯为原料或混合二氯苯为原料，原料成本大大降低。对-二氯苯硝化反应时几乎无副产物.
下面结合实施例作详细说明：
实施例1
第一步：在500ml玻璃三颈瓶中加入浓硝酸65g，浓硫酸75g，放在恒温水浴中升温至45～50℃；边搅拌边滴加邻二氯苯75g，半小时加完，再保温反应2小时结束。分去废酸，用30％碱酸中和一次，再加蒸馏水洗涤至中性，脱水得3.4-二氯硝基苯(Ⅲ)91.2g。含量97.5％，得率93％。废酸用100ml水稀释，分离得(Ⅲ)5.7g，总得率98.1％。
第二步：3.4-二氯硝基苯96g，加DMSO 140ml置于500ml二颈瓶中搅拌溶解，升温至120℃，缓慢加入干燥粉状的KF 60g，激烈揽拌，升温至190℃左右，回流反应约1小时；冷却至100℃，用水汽蒸馏，分离冷却固化后的馏出物，得3-氯-4-氟硝基苯(Ⅳ)72g，含量96.7％，收率83％。
第三步：干燥后的3-氯-4-氟硝基苯100g加入500ml三颈瓶中，加热至沸腾汽化，调节汽化量0.01mol/min，氯气从钢瓶中排出，通过流量计计量，调节为0.02mol/min，通入预热器预热至200℃，与3-Cl-4-FNB一起通入氯化反应管中进行反应，反应温度380℃。反应管出口即为2.4-二氯氟苯，反应管直径25mm，有效长度800mm，石英玻璃制成，反应管出口连接冷凝器。汽相产物在冷凝器内冷凝成液相，同时与多余的氯气分离。反应1小时，约得产物粗品61.4g，含量91.8％。三颈瓶中尚有3-氯-4-氟硝基苯约30g
该粗品经精馏后得2.4-二氯氟苯55.2g，含量99.1％。
实施例2
第一步：在500ml三颈瓶中加入浓硝酸70g，浓硫酸80g；放在恒温水浴上加入至50℃～55℃，边搅拌边滴加对-二氯苯(P-DCB)75g，半小时加完；恒温在55～60℃反应2小时结束，分去废酸，再经30％碱液中和，水洗，脱水得2.5-DCNB 90.6g；废酸用100ml水稀释，分离出2.5-DCNB 4.3g。共得产品94.9g，含量98.4％，得率97.03％。
第二步：2.5-DCNB 96g,DMS0 150ml，置于500ml三颈瓶中搅拌溶解，升温至120℃，缓慢加入KF 60g(干燥，粉状)，激烈搅拌，升温至约190℃.回流反应1小时；冷却至100℃，通入水汽进行蒸馏，结束后，分离冷却固化的馏出物，得2-F-5-CINB(Ⅶ)73.5g，含量95.8％，收率84％。
第三步：干燥的2-F-5-CINB 100g，加入500ml三颈瓶中，加热沸腾汽化，调节汽化量0.01mol/min；同时调节氯气流量为0.02mol/min并预热至200℃后，与2-F-5-CINB一起进入反应管反应。反应温度380℃反应管直径25mm，有效反应长度800mm，石英玻璃管制成，出口连一冷凝器。从反应管排出的产物，冷凝成液体与剩余氯分离，反应1小时，得2.4二氯氟苯粗产物61.5g，含量90.95％。
该粗品精馏后得2.4-二氯氟苯精品55g，含量＞98％。
实施例3
第一步：在1000ml三颈瓶中加入浓硝酸140g，浓硫酸160g，置于恒温水浴中加热至45～50℃，边搅拌边滴加混合二氯苯(其中0-占30％.P-占70％)150g，在一小时内加完，然后在50℃下恒温反应2小时0除去废酸，硝化物中和，洗涤，脱水，得混合二氯硝基苯181g，含量97.0％，得率92.3％，在废酸中加水150ml，分离出硝基物约10g，故总得率97.4％。
第二步：将第一步所得产物干燥后，取100g及DMSO 160ml加入1000ml三颈瓶中搅拌溶解，升温至120℃，缓慢加入干燥粉状KF 60g，激烈搅拌，升温至190℃，回流反应1小时。冷却至100℃，通入水蒸汽进行蒸馏，蒸馏结束分离冷却固化的馏出物，得混合氟氯硝基苯77g，含量97.2％。
第三步：将第二步的产物100g，加入500ml三颈瓶中，加热汽化，调节汽化量0.01mol/min；调节氯气流量为0.02mol/min，将之预热至200℃后，一起通入反应管进行反应，反应温度400℃。反应管与例1,2相同。反应1小时，得2.4-二氯氟苯62g，含量89.9％。
该粗品经精馏后得精品2.4-二氯氟苯54.5g，含量98.7％。
Claims (1)
1.一种2.4-二氯氟苯制备方法，其特征在于：
第一步，浓硝酸65～70g，浓硫酸70～80g，在恒温条件下，升温至45～55℃，边搅拌边加入邻二氯苯75g，硝化反应结束后，分离废酸，用液碱中和，再水洗至中性，脱水干燥后得3.4～二氯硝基苯；
第二步，96g3.4～二氯硝基苯加140～150ml二甲基亚砜，搅拌溶解，缓慢加入氟化钾60g，氟化反应后，用水汽蒸馏得3-氯-4-氟硝基苯粗品，再经真空精馏得3-氯-4-氟硝基苯纯品；
第三步，100g汽化的3氯-4-氟硝基苯与氯气一起通入管式反应器，反应温度为380～400℃氯化反应结束后得2.4-二氯氟苯粗品，再经真空脱除氯和二氧化氮，然后，精馏提纯得含量大于98％的2.4-二氯氟苯。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94120005A CN1044899C (zh) | 1994-12-29 | 1994-12-29 | 2.4－二氯氟苯制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94120005A CN1044899C (zh) | 1994-12-29 | 1994-12-29 | 2.4－二氯氟苯制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117038A CN1117038A (zh) | 1996-02-21 |
| CN1044899C true CN1044899C (zh) | 1999-09-01 |
Family
ID=5039451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94120005A Expired - Fee Related CN1044899C (zh) | 1994-12-29 | 1994-12-29 | 2.4－二氯氟苯制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1044899C (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906043B (zh) * | 2010-08-19 | 2013-06-12 | 江苏隆昌化工有限公司 | 一种溶剂洗涤法提纯高纯度2,5-二氯硝基苯的生产工艺 |
| CN101906044B (zh) * | 2010-08-19 | 2013-04-24 | 江苏隆昌化工有限公司 | 利用固废氯化苯焦油中提取的对二氯苯合成2,5-二氯硝基苯 |
| CN104649910B (zh) * | 2013-11-25 | 2017-01-11 | 江苏扬农化工集团有限公司 | 一种酸套用连续化硝化制备2,5-二氯硝基苯的方法 |
| CN105130744B (zh) * | 2015-08-19 | 2017-03-29 | 浙江林江化工股份有限公司 | 一种2,4‑二氟‑3,5‑二氯硝基苯合成1,3,5‑三氯‑2,4,6‑三氟苯 |
| CN105330605B (zh) * | 2015-11-22 | 2017-08-22 | 内蒙古佳瑞米精细化工有限公司 | 一种2‑甲巯基‑4,6‑二氟嘧啶的工业化生产方法 |
| CN114105726B (zh) * | 2021-12-15 | 2024-01-19 | 江苏三美化工有限公司 | 一种2，4-二氯三氟甲苯的制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4582946A (en) * | 1979-10-04 | 1986-04-15 | Henkel Corporation | Polyhydric alcohols |
| US4898996A (en) * | 1987-03-25 | 1990-02-06 | Nippon Kayaku Kabushiki Kaisha | Process for producing 3-chloro-4-fluoronitrobenzene |
-
1994
- 1994-12-29 CN CN94120005A patent/CN1044899C/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4582946A (en) * | 1979-10-04 | 1986-04-15 | Henkel Corporation | Polyhydric alcohols |
| US4898996A (en) * | 1987-03-25 | 1990-02-06 | Nippon Kayaku Kabushiki Kaisha | Process for producing 3-chloro-4-fluoronitrobenzene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1117038A (zh) | 1996-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4489210A (en) | Process for the halogenation of organic compounds | |
| US4735747A (en) | Process and apparatus for the photochemical sulphochlorination of gaseous alkanes | |
| US2739174A (en) | Nitrating aromatic hydrocarbons with only nitric acid | |
| CN1044899C (zh) | 2.4－二氯氟苯制备方法 | |
| KR102067307B1 (ko) | 단열 니트로화에 의한 니트로벤젠의 제조방법 | |
| IE51947B1 (en) | Process for the preparation of orthotrifluoromethyl-aniline | |
| US5683553A (en) | Preparation of 3-chlorophthalic anhydride | |
| US5227545A (en) | Process for the preparation of 2,4-dichlorofluorobenzene | |
| KR100375905B1 (ko) | 디니트로톨루엔의제조방법 | |
| CA2155561A1 (en) | Process for the production of dinitrotoluene | |
| US2608591A (en) | Substitution chlorination of aromatic compounds with liquid chlorine | |
| US5245092A (en) | Process for preparing dinitrotoluene with low by-product content | |
| CA2361209A1 (en) | Continuous isothermal process for preparing mononitrotoluenes | |
| US5006325A (en) | Process for the recovery of nitric acid | |
| CN1258519C (zh) | 一种联产3－氯－4－氟苯胺和2,6－二氯氟苯的方法 | |
| KR940011129B1 (ko) | 3-클로로-4-플루오로니트로벤젠의 제법 | |
| JPS63162634A (ja) | 置換３．５‐ジクロロ‐２，４‐ジフルオロベンゼンの製造方法 | |
| US2499629A (en) | Photochemical manufacture of 1,1,1-difluorochloroethane | |
| RU2293722C9 (ru) | Способ непрерывного изотермического получения мононитротолуолов в присутствии фосфорной кислоты | |
| US4089909A (en) | Separation of dichlorobenzene isomers | |
| US4306103A (en) | Process for the manufacture of 1,3,5-trichlorobenzene | |
| CN1034999C (zh) | 一种1，1，1-三氟-2，2，2-三氯乙烷的制备方法 | |
| EP0378366B1 (en) | Preparation of 2-chloroterephthaloyl chloride | |
| US3206378A (en) | Purification of mixed isomers of dicyanobenzenes by vacuum distillation | |
| DE19544870C2 (de) | Verfahren zur Herstellung von 1-Brom-3,5-difluorbenzol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |