CN1339428A - 邻位取代的苯甲醛、它的制备方法和用途 - Google Patents
邻位取代的苯甲醛、它的制备方法和用途 Download PDFInfo
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title description 8
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- 239000003814 drug Substances 0.000 claims abstract description 4
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- 239000011877 solvent mixture Substances 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
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- 150000002900 organolithium compounds Chemical class 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
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- JCIVHYBIFRUGKO-UHFFFAOYSA-N lithium;2,2,6,6-tetramethylpiperidine Chemical compound [Li].CC1(C)CCCC(C)(C)N1 JCIVHYBIFRUGKO-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- UHBXGHADNVDXMM-UHFFFAOYSA-N C(C)(C)N(C(C)C)CC[Li] Chemical compound C(C)(C)N(C(C)C)CC[Li] UHBXGHADNVDXMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 125000001792 phenanthrenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims 1
- 150000002642 lithium compounds Chemical class 0.000 abstract description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 abstract description 3
- 150000005171 halobenzenes Chemical class 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- -1 Phenyl aldehyde Chemical class 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- PJNILWKRAKKEQM-UHFFFAOYSA-N 2-bromo-6-fluorobenzaldehyde Chemical compound FC1=CC=CC(Br)=C1C=O PJNILWKRAKKEQM-UHFFFAOYSA-N 0.000 description 1
- OACPOWYLLGHGCR-UHFFFAOYSA-N 2-chloro-6-fluorobenzaldehyde Chemical compound FC1=CC=CC(Cl)=C1C=O OACPOWYLLGHGCR-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- CLITVQODSQZPEQ-UHFFFAOYSA-N CCCCCC1=CC=C(C=C1)C2=CC=CC=C2CCOF Chemical group CCCCCC1=CC=C(C=C1)C2=CC=CC=C2CCOF CLITVQODSQZPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 238000003747 Grignard reaction Methods 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
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- 230000008025 crystallization Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- HTZGVHYSMVGNOV-UHFFFAOYSA-N lithium;dicyclohexylazanide Chemical compound [Li+].C1CCCCC1[N-]C1CCCCC1 HTZGVHYSMVGNOV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UNBDDZDKBWPHAX-UHFFFAOYSA-N n,n-di(propan-2-yl)formamide Chemical compound CC(C)N(C=O)C(C)C UNBDDZDKBWPHAX-UHFFFAOYSA-N 0.000 description 1
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- GBDYFPAHVXJQEP-UHFFFAOYSA-N n-ethyl-n-phenylformamide Chemical compound CCN(C=O)C1=CC=CC=C1 GBDYFPAHVXJQEP-UHFFFAOYSA-N 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- VFJYIHQDILEQNR-UHFFFAOYSA-M trimethylsulfanium;iodide Chemical compound [I-].C[S+](C)C VFJYIHQDILEQNR-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
式(I)的化合物，它是通过在溶剂或溶剂混合物中、在－60℃以下的温度下,将式(II)卤代苯与有机锂化合物反应,然后与式(III)甲酰基等同物反应来制备的,该化合物可用作制备农用化学品、电子材料和药品的起始原料。
Description
在化学文献中对作为用于活性物质合成的起始原料(例如，EP-A-0174 131，EP-A-0 271 240，EP-A-0 289 942，FR-A-1 514 517，US-A-3856 504，US-A-3 982 020US-A-4 902 814)或一般作为中间体(DE-A3 310 953)的、有邻位卤素取代基或有总共至多5个取代基的苯甲醛进行了广泛的描述。以2-氯-6-氟苯甲醛，2-溴-6-氟苯甲醛和2-氟-6-碘苯甲醛形式存在的、在一个邻位上具有氯、溴或碘取代基和在另一个邻位上具有氟取代基的醛是已知的。然而，对具有多个氟取代基和其它官能团的化合物存在着需求，因为氟化或不同程度的氟化通过改变亲油性和/或偶极距经常会增强农用化学品或药品的活性(Kanie等人，Bull.Chem.Soc.Jpn.(日本化学协会简报)2000，73，471)。
具有多个氟取代基-其中一个与醛官能团相邻-和邻位卤素取代基(不是氟)的苯甲醛是未知的，尽管这些化合物中的一些能够从上述参考文献的通式中得出。
因此本发明提供了式(I)的邻位取代苯甲醛：
其中X1，X2和Y具有以下含义：
X1＝H或F
X2＝H或F
Y＝Cl，Br或I。
优选下面的化合物：
a)X1和X2是H
Y是Cl或Br；或
b)X1是F，X2是H
Y是Cl或Br；或
c)X1和X2是F
Y是Cl或Br；
尤其为
2-氯-5，6-二氟苯甲醛
2-氯-5，6-二氟苯甲醛
2-氯-4，5，6-三氟苯甲醛
2-溴-4，5，6-三氟苯甲醛。
本发明而且提供了制备式(I)化合物的方法，它包括，在溶剂或溶剂混合物中、在不促进阿林(arine)形成的温度下，使其中Y，X1和X2如式(I)所定义的式(II)的卤代苯与有机锂化合物反应。锂化合物与起始原料(II)的摩尔比优选是1∶1-1.2∶1，所得到的锂化合物然后再次在不促进阿林(arine)形成的温度下与式(III)的甲酰基等同物反应，随后水解得到(I)。(II)与(III)的摩尔比优选是1∶1-1∶2。
在(III)中，R1具有1-6个碳原子的烷基，三甲基甲硅烷基或(取代或未取代的)苯基，R2是具有1-6个碳原子的烷基，三甲基甲硅烷基或(取代或未取代的)苯基，和R3是-CH(＝O)或-CH(OR4)2；R1和2与氮原子一起还可以是五元到七元环的一部分。R4是具有1-4个碳原子的烷基。
式(II)化合物与有机锂化合物的反应优选在-60℃以下的温度下，尤其优选在-70℃以下的温度下，更尤其在-70C到-110℃的温度下进行。典型的反应时间是1-8小时。当反应结束时(例如可通过DC或GC检测)，将反应混合物缓慢升温到-25℃到-15℃，仔细用水进行水解。使用盐酸将混合物酸化到pH为1-5，并用适合的溶剂(例如，叔丁基甲基醚，二氯甲烷，乙酸乙酯，甲苯)萃取。合并有机相的提取物，例如用硫酸钠进行干燥。在减压下除去溶剂，以得到所需的式(III)邻位取代的苯甲醛，如果需要，产物能够通过液相色谱法、蒸馏或结晶或它们的结合来纯化。典型的收率是在50-80％的范围内，基于(II)计。有机锂化合物优选是仲胺的锂化合物，尤其具有大的取代基。尤其优选二异丙基氨基化锂，2，2，6，6-四甲基哌啶锂，二环己基氨基化锂，环己基异丙基氨基化锂或双(三甲基甲硅烷基)氨基化锂。尤其，优选2，2，6，6-四甲基哌啶锂。对于那些其中Y是Cl的式(II)化合物，有机锂化合物是烷基锂化合物或仲胺的锂化合物；优选正丁基锂。如果需要，可以加入叔丁醇钾以改善活化。
在优选的实施方案中，式(II)中的Y是Br。理想的是，将活化剂或选择性改性剂加到反应混合物中，例如四甲基乙二胺或叔丁醇钾(后者对于那些其中Y是Cl的式(II)化合物是优选的)。
式(III)的甲酰基等同物优选是N，N-二甲基甲酰胺，N，N-二乙基甲酰胺，N，N-二乙基甲酰胺，N，N-二丙基甲酰胺，N，N-二异丙基甲酰胺，N，N-二丁基甲酰胺，N-甲酰基吡咯烷酮，N-甲酰基吗啉，N-甲酰基哌啶，二甲基甲酰胺二烷基乙酰，N-甲基甲酰苯胺，N-乙基甲酰苯胺或N，N-双(三甲基甲硅烷基)甲酰胺。
式(III)的甲酰基等同物尤其优选N，N-二甲基甲酰胺。
用于本发明的适合溶剂是质子惰性溶剂，例如醚如四氢呋喃、1，2-二甲氧基乙烷、1，4-二噁烷、乙醚，或者烃如己烷、环己烷、庚烷、戊烷或这些质子惰性溶剂的混合物。
(II)与有机锂化合物的反应也能够在化合物(III)的存在下进行，以便从(II)原位形成的锂衍生物能够直接与(III)反应。为此，在-60℃以上，例如在-20到+25℃的范围内进行反应是必要和理想的。
本发明而且提供了式(I)的化合物作为制备农用化学品，电子材料，尤其液晶，以及药品的起始原料的用途。式(I)的化合物尤其适合于这些目的，因为醛官能团(例如，经Witting反应，还原得到苄基醇，与C-H、N-H或S-H化合物缩合)和卤素官能团(这里指取代基Y的官能团)(例如经Suzuki偶联，Grignard反应，Heck反应)可为反应所利用，以及有可能在其中X1是F的那些化合物或由它衍生的产物的情况下，更尤其在其中X1和X2是F的那些化合物或由它衍生的产物的情况下的特定条件下，可利用二氟芳族化合物(例如，经邻位金属取代)或三氟芳族化合物(例如，经邻位金属取代或芳族亲核取代)或四氟芳族化合物(例如，经芳族亲核取代)的反应活性。
实施例：
实施例1 2-溴-5，6-二氟苯甲醛
152mmol的2，2，6，6-四甲基哌啶和152mmol的正丁基锂(在正己烷中的1.6M溶液)在280ml干燥四氢呋喃中的溶液在-75℃下与145mmol的1-溴-3，4-二氟苯混合。保持该温度4小时，然后滴加174mmol的DMF。然后缓慢解冻该反应混合物，用水在-20℃下水解，使用盐酸酸化，和用叔丁基甲基醚萃取。用饱和氯化钠溶液洗涤所合并的有机萃取物，并使用硫酸钠干燥。在减压下除去该溶剂，粗产物通过液相色谱法在硅胶上纯化(洗脱剂：二氯甲烷/正庚烷1∶1)和从正庚烷中重结晶，得到呈微黄色晶体的18g(56％)2-溴-5，6-二氟苯甲醛。熔点：40-43.5℃。1H-NMR(400MHz，CDCl3/TMS)：δ＝10.31(dd，4J(HF)＝2Hz，5J(HF)＝1.5Hz，1H，CHO)，7.45(ddd，3J(HH)＝9Hz，4J(HF)＝4Hz，5J(HF)＝2Hz，1H，Har)，7.28(ddd，3J(HF)＝9Hz，4J(HF)＝8Hz 1H，Har)。19F-NMR(376.5MHz，1H宽带去耦，CDCl3/CFCl3)：δ＝-136.4(d，3J＝19.2Hz)，-139.2(d，3J＝19.2Hz)。
实施例2
2-溴-4，5，6-三氟苯甲醛能够以与实施例1相似的方式从1-溴-3，4，5-三氟苯起始来获得。1H-NMR(400MHz，CDCl3/TMS)：δ＝10.24(dd，4J(HF)＝1.5Hz，5J(HF)＝1Hz，1H，CHO)，7.38(ddd，3J(HH)＝9Hz，4J(HF)＝6Hz，5J(HF)＝2Hz，1H，Har)，19F-NMR(376.5MHz，1H宽带去耦，CDCl3/CFCl3)：δ＝-123.4(dd，3J＝20Hz和13Hz)，-135.9(dd，3J＝19Hz和13Hz)，-158.0(dd，3J＝19Hz和13Hz)。
实施例3
2-氯-5，6-二氟苯甲醛能够与实施例1相似从1-氯-3，4-二氟苯起始来获得。
实施例4
2-溴-3，4，5，6-四氟苯甲醛能够与实施例1相似从1-溴-2，3，4，5-四氟苯起始来获得。
实施例5
2-氯-3，4，5，6-四氟苯甲醛能够与实施例1相似从1-氯-2，3，4，5-四氟苯起始来获得。
实施例6
2-碘-5，6-二氟苯甲醛能够与实施例1相似从3，4-二氟苯起始来获得。
应用实施例1根据Kumar，有机化学期刊1997，62，8535-8539页中所述，将2-溴-5，6-二氟苯甲醛与4-戊基苯基硼酸在Pd催化剂的存在下反应，以得到3，4-二氟-4’-戊基二苯基-2-羧醛(carbaldehyde)。该化合物根据Kumar，上文所述与三甲基碘化锍反应，以得到3，4-二氟-2-(环氧乙烷-1-基)-4’-戊基联苯。无需进一步纯化，该化合物在BF3醚合物的存在下被转化为1，2-二氟-7-戊基菲。粗产品通过一般用于这种液晶材料的工序来纯化(参考DE-A 195 00 768)，产生呈无色晶体的1，2-二氟-7-戊基菲。
Claims (13)
1、式(I)的化合物：
其中X1，X2和Y具有以下含义：
X1＝H或F，
X2＝H或F，
Y＝Cl，Br或I。
2、权利要求1所要求的化合物，其中：
a)X1和X2是H
Y是Cl或Br；或
b)X1是F，X2是H
Y是Cl或Br；或
c)X1和X2是F，
Y是Cl或Br。
3、制备权利要求1或2所要求的化合物的方法，其特征在于，在溶剂或溶剂混合物中、在-60℃以下的温度下，使其中Y，X1和X2如权利要求1所定义的式(II)卤代苯与有机锂化合物反应，然后与式(III)甲酰基等同物反应，随后水解：
其中在(III)中，R1具有1-6个碳原子的烷基，三甲基甲硅烷基或(取代或未取代的)苯基，R2是具有1-6个碳原子的烷基，三甲基甲硅烷基或(取代或未取代的)苯基，和R3是-CH(＝O)或-CH(OR4)2，其中R1和R2与氮原子一起还可以是五元到七元环的一部分，R4是具有1-4个碳原子的烷基。
4、权利要求3所要求的方法，其特征在于，温度是在-70℃以下。
5、权利要求3或4所要求的方法，其特征在于，所述式(III)的化合物是二甲基甲酰胺或二乙基甲酰胺。
6、在前述权利要求3-5中的至少一项中所要求的方法，其特征在于，所述有机锂化合物是2，2，6，6-四甲基哌啶锂或二异丙基氨基化锂或当Y＝Cl时是烷基锂。
7、在前述权利要求3-6中任一项中所要求的方法，其特征在于，将活化剂或选择性改性剂，尤其四亚甲基二胺或叔丁醇钾加到反应混合物中。
8、在前述权利要求3-7中的至少一项中所要求的方法，其特征在于，所述式(II)的化合物与所述有机锂化合物在式(III)化合物的存在下反应。
9、权利要求8所要求的方法，其特征在于，反应在-25℃到+25℃范围内的温度下进行。
10、在前述权利要求3-9中的至少一项中所要求的方法，其特征在于，所述式(I)的化合物以50-80％的收率获得。
11、权利要求1或2所要求的化合物作为用于制备农用化学品、电子材料和药品的起始原料的用途。
12、权利要求11所要求的用途，其特征在于，所述电子材料是液晶混合物的组分。
13、权利要求12所要求的用途，其中所述液晶混合物的组分是菲衍生物。
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| DE10022661A DE10022661A1 (de) | 2000-05-10 | 2000-05-10 | Ortho-substituierte Benzaldehyde, Verfahren zu ihrer Herstellung und ihre Verwendung |
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| EP (1) | EP1153909B1 (zh) |
| JP (1) | JP2001316323A (zh) |
| KR (1) | KR100758518B1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659546A (zh) * | 2012-05-03 | 2012-09-12 | 江苏泰特尔化工有限公司 | 一种新型的液晶中间体4-溴-2,3-二氟苯甲醛 |
| CN105967974A (zh) * | 2016-05-06 | 2016-09-28 | 蚌埠中实化学技术有限公司 | 一种2-甲基-3,4,5-三氟溴苯的制备方法 |
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| DE10225048B4 (de) * | 2001-06-07 | 2015-03-12 | Merck Patent Gmbh | Fluorierte (Dihydro)phenanthrenderivate und deren Verwendung in flüssigkristallinen Medien |
| DE10145780B4 (de) | 2001-09-17 | 2012-10-04 | Merck Patent Gmbh | Fluorierte Cyclopenta[a]naphthaline und ihre Verwendung in Flüssigkristallmischungen und Displays |
| DE10145779B4 (de) * | 2001-09-17 | 2012-11-15 | Merck Patent Gmbh | Fluorierte Cyclopenta[b]naphthaline und ihre Verwendung in Flüssigkristallmischungen |
| US6677479B2 (en) | 2001-11-13 | 2004-01-13 | Clariant Finance Lbvi Limited | Substituted fluoroaromatics, process for preparing them and their use |
| DE102004022728B4 (de) * | 2004-05-07 | 2018-08-23 | Merck Patent Gmbh | Fluorierte Phenanthrene und ihre Verwendung in Flüssigkristallmischungen |
| CN102659544A (zh) * | 2012-05-02 | 2012-09-12 | 上海中新裕祥化工有限公司 | 2，3-二氟苯甲醛的制备方法 |
| CN104447250A (zh) * | 2014-12-24 | 2015-03-25 | 常熟市新华化工有限公司 | 一种由对氯甲苯合成对氯苯甲醛的方法 |
| CN111018892A (zh) * | 2020-01-03 | 2020-04-17 | 烟台盛华液晶材料有限公司 | 一种芳烃氟邻位金属化的制备方法 |
| CN115010574B (zh) * | 2022-06-06 | 2024-01-05 | 爱斯特（成都）生物制药股份有限公司 | 1-溴-2-氯-4-氟-2碘苯的合成方法 |
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| CH471196A (de) | 1966-04-06 | 1969-04-15 | Basf Ag | Verfahren zur Herstellung eines orangen Pigmentfarbstoffs |
| FR1514517A (fr) | 1967-03-08 | 1968-02-23 | Ile De France | Procédé de préparation de dérivés de n-substitués benzamides |
| US3982020A (en) | 1970-03-17 | 1976-09-21 | Sandoz, Inc. | Substituted benzylidene hydrazines for treating hyperglycemia, obesity and inflammation |
| US3856504A (en) | 1971-06-08 | 1974-12-24 | Hercules Inc | Use of certain n-(2,6-dihalobenzylidene)-benzylamines and certain n-(2,6-dihalobenzylidene)phenylethylamines to increase crop yield |
| DE3310953A1 (de) | 1983-03-25 | 1984-09-27 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von benzalchloriden |
| EP0174131A3 (en) | 1984-09-01 | 1989-06-07 | FISONS plc | Dihydropyridines, processes and intermediates for their production, and pharmaceutical formulations containing them |
| AU6042686A (en) * | 1985-07-29 | 1987-02-05 | American Home Products Corporation | 1,4,5,6,7,8-hexahydro-(substituted) phenyl-1,7- napthyridine-3-carboxylic acid derivatives |
| GB8617649D0 (en) | 1986-07-18 | 1986-08-28 | Ici Plc | Fluorobenzyl esters |
| GB8629806D0 (en) | 1986-12-12 | 1987-01-21 | Ici Plc | Fluorobenzyl esters |
| DE3882167T2 (de) | 1987-05-08 | 1994-04-07 | Ihara Chemical Ind Co | Verfahren zur Herstellung von Fluorbenzaldehyden. |
| US5340833A (en) * | 1992-05-01 | 1994-08-23 | Eisai Co., Ltd. | Urokinase inhibitors |
| DE19500768C2 (de) | 1994-01-17 | 2003-11-20 | Aventis Res & Tech Gmbh & Co | Phenanthren-Derivate und ihre Verwendung in flüssigkristallinen Mischungen |
| US5648021A (en) | 1994-01-17 | 1997-07-15 | Hoechst Aktiengesellschaft | Phenanthrene derivatives and their use in liquid-crystalline mixtures |
| UA56185C2 (uk) * | 1996-09-30 | 2003-05-15 | Пфайзер Інк. | Аралкіл- та аралкіліденгетероциклічні лактами та іміди, фармацевтична композиція та спосіб лікування |
| GB0005789D0 (en) * | 2000-03-11 | 2000-05-03 | Knoll Ag | Therapeutic agents |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102659546A (zh) * | 2012-05-03 | 2012-09-12 | 江苏泰特尔化工有限公司 | 一种新型的液晶中间体4-溴-2,3-二氟苯甲醛 |
| CN105967974A (zh) * | 2016-05-06 | 2016-09-28 | 蚌埠中实化学技术有限公司 | 一种2-甲基-3,4,5-三氟溴苯的制备方法 |
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| Publication number | Publication date |
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| EP1153909A3 (de) | 2002-07-24 |
| KR20010104657A (ko) | 2001-11-26 |
| EP1153909B1 (de) | 2004-10-13 |
| JP2001316323A (ja) | 2001-11-13 |
| KR100758518B1 (ko) | 2007-09-14 |
| US6811832B2 (en) | 2004-11-02 |
| CN1170804C (zh) | 2004-10-13 |
| DE10022661A1 (de) | 2001-11-15 |
| EP1153909A2 (de) | 2001-11-14 |
| US20010050352A1 (en) | 2001-12-13 |
| DE50104070D1 (de) | 2004-11-18 |
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