CN115124430A - 一种2,2'-二(三氟甲基)二氨基联苯的合成工艺 - Google Patents
一种2,2'-二(三氟甲基)二氨基联苯的合成工艺 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 17
- YGNISOAUPSJDJE-UHFFFAOYSA-N 4-bromo-3-(trifluoromethyl)aniline Chemical compound NC1=CC=C(Br)C(C(F)(F)F)=C1 YGNISOAUPSJDJE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- 230000008878 coupling Effects 0.000 claims abstract description 4
- 238000010168 coupling process Methods 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- UCWBKJOCRGQBNW-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;dihydrate Chemical compound O.O.[Na+].OCS([O-])=O UCWBKJOCRGQBNW-UHFFFAOYSA-M 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 150000003857 carboxamides Chemical class 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 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
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
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- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
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- 238000003756 stirring Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- SXEQQBBOAMHOID-UHFFFAOYSA-N 1-bromo-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C(C(F)(F)F)=C1 SXEQQBBOAMHOID-UHFFFAOYSA-N 0.000 description 3
- IQMVQGPUTBIFQE-UHFFFAOYSA-N 4-nitro-1-[4-nitro-2-(trifluoromethyl)phenyl]-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC([N+](=O)[O-])=CC=C1C1=CC=C([N+]([O-])=O)C=C1C(F)(F)F IQMVQGPUTBIFQE-UHFFFAOYSA-N 0.000 description 3
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- 230000002194 synthesizing effect Effects 0.000 description 3
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 3
- NDOOLCPFQSTTNC-UHFFFAOYSA-N 1,2-diphenyl-1-(trifluoromethyl)hydrazine Chemical compound FC(F)(F)N(NC1=CC=CC=C1)C1=CC=CC=C1 NDOOLCPFQSTTNC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- JSWQDLBFVSTSIW-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl]hydrazine Chemical compound NNC1=CC=CC=C1C(F)(F)F JSWQDLBFVSTSIW-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- WHNAMGUAXHGCHH-UHFFFAOYSA-N 1-nitro-3-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=CC(C(F)(F)F)=C1 WHNAMGUAXHGCHH-UHFFFAOYSA-N 0.000 description 1
- RGUGZPYYMOAJLO-UHFFFAOYSA-N 2,3,6-trifluoroaniline Chemical compound NC1=C(F)C=CC(F)=C1F RGUGZPYYMOAJLO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
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- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种2,2’‑二(三氟甲基)二氨基联苯的合成工艺,以间氨基三氟甲苯为起始物料,经溴化得到3‑三氟甲基‑4‑溴苯胺,然后与间氨基三氟甲苯在Rongalite试剂和碱作用下,偶联得到最终产品2,2’‑二(三氟甲基)二氨基联苯。本发明的2,2’‑二(三氟甲基)二氨基联苯的合成工艺成本低,三废少,收率高,工艺过程简单,反应条件温和,适合工业化放大生产。
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种2,2'-二(三氟甲基)二氨基联苯的合成工艺。
背景技术
2,2' -二(三氟甲基)-4, 4'-二氨基联苯(简称TFMB,下同),是合成高性能聚酰亚胺树脂的重要单体。聚酰亚胺是指主链上含有酰亚胺环(-CO-N-CO-)的一类聚合物,通常是由芳香族二元伯胺与芳香族二元酐通过缩聚反应而获得的。以TFMB为单体合成的聚酰亚胺,因为引入了氟基团,氟元素具有很小的原子半径和很高的电负性, 使得聚酰亚胺在保留优良综合性能的同时含有其他许多独特的性能,因此用TFMB合成的聚酰亚胺树脂具有热稳定性高、绝缘性好、耐磨损、抗老化、耐化学药品性﹑耐辐射性能, 以及良好的韧性和柔软性,已广泛应用在航空航天、电子、电气、纳米、液晶、分离膜、激光、精密机械等领域。
目前工业上,2,2' -二(三氟甲基)-4, 4'-二氨基联苯合成方法主要是以下两种:
方法一:由间硝基三氟甲苯合成3,3'-双(三氟甲基)肼苯,再经过重排反应得到2,2' -二(三氟甲基)-4, 4'-二氨基联苯,路线如下:
专利CN101525294A公开了一种2,2' -双(三氟甲基)-4,4'-二氨基联苯的制备方法,其使用醇和芳烃混合溶剂,Zn粉还原制备3,3'-双(三氟甲基)肼苯,经酸化、过滤后在无机酸条件下重排反应,分液回收溶剂,重结晶得到2,2'-双(三氟甲基)-4,4'-二氨基联苯;虽然所用的溶剂可回收,但是总收率不高,另外采用Zn粉还原,会产生大量三废,不够环保。专利CN109232273A也公开了一种2,2' -双(三氟甲基)-4,4'-二氨基联苯的制备方法,其制备方法中第一步在无机碱水溶液中,以相转移催化利、助催化剂及Pd/C为催化体系,芳烃作为溶剂,合成3,3'-双(三氟甲基)二苯肼,第二步将3,3'-双(三氟甲基)二苯肼在无机酸水溶液条件下,重排反应得到2,2' -双(三氟甲基)-4,4'-二氨基联苯;虽然避免了锌粉,但Pd/C价格昂贵,成本较高,且第二步还是要使用大量的强酸,产生大量三废,因此该合成方法也不适合大量生产。
方法二:由2-溴-5-硝基三氟甲苯偶联得到2,2'-双(三氟甲基)-4,4'-二硝基联苯,再经过还原得到2,2' -二(三氟甲基)-4, 4'-二氨基联苯,路线如下:
专利CN101337895A公开了2,2'-双(三氟甲基)-4,4'-二硝基联苯的制备方法,利用以2-溴-5-硝基三氟甲苯为原料,在过渡金属(Pd,Cu,Ni)的催化下进行偶联反应,获得2,2'-双(三氟甲基)-4,4'-二硝基联苯,再经Cu的氧化物或金属Pd/C的催化加氢获得2,2'-双(三氟甲基)-4,4'-二氨基联苯。该方法优点在于:三废少,利于环保。但缺点在于:(1)原料2-溴-5-硝基三氟甲苯价格高,原料成本高;(2) 金属催化剂用量大,三废高,且反应在155℃高温度下进行,易产生副反应,产品纯度低。
因此针对TFMB的制备,研发一种安全、环保、低成本﹑操作简便、适合工业化生产的工艺具有非常重要的价值。
发明内容
本发明的目的是提供一种收率高、成本低、三废少、适合工业化生产的2,2'-二(三氟甲基)二氨基联苯的合成工艺。
本发明解决上述问题所采用的技术方案为:一种2,2’-二(三氟甲基)二氨基联苯的合成工艺,合成路线为:
包括以下步骤:
(1)以间氨基三氟甲苯(化合物I)为起始物料,经溴化试剂溴化得到3-三氟甲基-4-溴苯胺(化合物Ⅱ);
(2)3-三氟甲基-4-溴苯胺与间氨基三氟甲苯在羟基甲亚磺酸单钠盐二水合物(Rongalite)试剂和碱作用下,偶联得到2,2’-二(三氟甲基)二氨基联苯(化合物Ⅲ)。
优选的,步骤(1)中所述溴化试剂为N-溴代琥珀酰亚胺(NBS)、溴素、二溴海因中至少一种。
优选的,步骤(1)中所述溴化试剂与间氨基三氟甲苯的摩尔比为0.5-2.0:1。
优选的,所述步骤(1)在溶剂体系中进行,所述溶剂为二氯甲烷、甲苯、有机酰胺类溶剂、有机醚类溶剂、无机酸中至少一种。
优选的,步骤(2)中所述碱性物质为氢氧化钾、氢氧化钠、氢氧化锂、叔丁醇钠、叔丁醇钾、碳酸钠、碳酸钾、碳酸铯、碳酸氢钠、碳酸氢钾、甲醇钠、甲醇钾、二异丙基乙基胺中至少一种。
优选的,步骤(2)中所述碱性物质与3-三氟甲基-4-溴苯胺的摩尔比为0.5-3.0:1。
优选的,所述步骤(2)在溶剂体系中进行,所述溶剂为二甲基亚砜、有机酰胺类溶剂、有机醚类溶剂、有机醇类溶剂、二氯甲烷中至少一种。
优选的,步骤(1)的反应温度为20-30oC,反应时间2-5h。
优选的,步骤(2)的反应温度为75-85oC,反应时间12-18h。
与现有技术相比,本发明的优点在于:
(1)本发明所用原料便宜,不需要使用较贵的金属试剂,大大降低了生产成本,其中Rongalite(羟基甲亚磺酸单钠盐二水合物)试剂,是一种廉价的工业用于橡胶、纺织和染料工业的产品。
(2)本发明无需使用大量有机酸,且排放三废少,环保。
(3)本发明的2,2’-二(三氟甲基)二氨基联苯的合成工艺操作过程简单,反应条件温和,易分离纯化,收率高,适合工业化放大生产。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1
步骤(1):制备3-三氟甲基-4-溴苯胺
向带有磁力搅拌器的3 L三口瓶中加入100g(621mmol)间氨基三氟甲苯、500mLDMF,置换氮气,然后降温至5℃;在1L三口瓶中加入55.3g(311mmol)NBS和500mL DMF,搅拌溶解,然后将其滴加到上述3L三口瓶中,保持温度在5-10℃,滴加结束后升温至25℃,25℃下搅拌反应3h;反应完毕加入水淬灭,再加入水和乙酸乙酯,搅拌分液,有机相用盐水洗涤后浓缩,使用甲苯-水重结晶,得到120.8g浅黄色固体3-三氟甲基-4-溴苯胺(理论量149g),收率81%。
1H NMR (CDCl3,400 MHz, ppm):δ7.38 (d, J = 8.8 Hz, 1H), 6.95(d, J = 2.8Hz, 1H), 6.63 (dd, J = 2 Hz, J =8.4 Hz, 1H), 3.84 (br s, 2H)。
步骤(2):制备2,2’-二(三氟甲基)二氨基联苯
向带有磁力搅拌器的3 L三口瓶中加入100g(417mmol)3-三氟甲基-4-溴苯胺、134g(834mmol)间氨基三氟甲苯,128.4g(834mmol)Rongalite(羟基甲亚磺酸单钠盐二水合物),46.7g(834mmol)KOH,置换氮气,加入1.5L二甲基亚砜;加入完毕后,升温至80℃,反应16小时;反应结束后将反应冷却至25℃,加入水,再用乙酸乙酯萃取3次,有机相合并浓缩,然后使用甲基叔丁基醚(MTBE)重结晶,得到86.7g白色粉末固体2,2’-二(三氟甲基)二氨基联苯(理论量133.5g),收率65%。
1HNMR(CDCl3, 400MHz, ppm):δ 7.16(d, J =7.2 Hz,2H), 6.78 (d, J =6.8 Hz,2H) , 6.52(d, J =6.4 Hz,2H), 4.0(d, J =4.0 Hz,4H)。
实施例2
步骤(1):制备3-三氟甲基-4-溴苯胺
向带有磁力搅拌器的3 L三口瓶中加入100 g(621 mmol)间氨基三氟甲苯、1000mL二氯甲烷,置换氮气,然后降温至5℃,滴加119.2g(745 mmol)溴素,保持温度在5-10℃,滴加结束后升温至25℃,25℃下搅拌反应3h;反应结束后加入水淬灭,再加入水和二氯甲烷,搅拌分液,有机相用盐水洗涤后浓缩,使用甲苯-水重结晶,得到113g 浅黄色固体3-三氟甲基-4-溴苯胺(理论量149g),收率76%。
1H NMR (CDCl3,400 MHz, ppm):δ7.52 (d, J = 8.4 Hz, 1H), 6.99 (d, J = 2Hz, 1H), 6.88 (dd, J = 2 Hz, J = 8.4 Hz, 1H), 4.31 (br s, 2H)。
步骤(2):制备2,2’-二(三氟甲基)二氨基联苯
向带有磁力搅拌器的3 L三口瓶中加入80g(333 mmol)3-三氟甲基-4-溴苯胺、107.4g(667 mmol)间氨基三氟甲苯,102.7g(667 mmol)Rongalite(羟基甲亚磺酸单钠盐二水合物),26.7g(667 mmol)NaOH ,置换氮气,加入1.2L 二甲基亚砜;加入完毕后,升温至80℃,反应16小时;将反应冷却至25℃,加入水,再用乙酸乙酯萃取3次,有机相合并浓缩,然后使用甲基叔丁基醚(MTBE)重结晶,得到65.1g白色粉末固体2,2’-二(三氟甲基)二氨基联苯(理论量106.7g),收率61%。
1HNMR(CDCl3, 400MHz, ppm):δ 7.18(d, J =7.2 Hz,2H), 6.83 (d, J =6.8 Hz,2H) , 6.55(d, J =6.4 Hz,2H), 4.0(d, J =4.0 Hz,4H)。
实施例3
步骤(1):制备3-三氟甲基-4-溴苯胺
向带有磁力搅拌器的3 L三口瓶中加入100 g(621 mmol)间氨基三氟甲苯、500mL浓硫酸,然后降温至10℃,分批加入94.1g(329mol)二溴海因有明显放热,保持温度在10-15℃,加完后升温至25℃,25℃下搅拌反应5小时;反应结束后缓慢滴加水淬灭,并控制温度小于45℃,滴加完毕后降温至25℃,搅拌2小时过滤,滤饼用甲苯-水重结晶,得到119g 浅黄色固体3-三氟甲基-4-溴苯胺(理论量149g),收率80%。
1H NMR (CDCl3,400 MHz, ppm):δ7.50 (d, J = 8.8 Hz, 1H), 6.97 (d, J = 2Hz, 1H), 6.75 (dd, J = 2 Hz, J = 8.4 Hz, 1H), 4.12 (br s, 2H)。
步骤(2):制备2,2’-二(三氟甲基)二氨基联苯
向带有磁力搅拌器的3 L三口瓶中加入110g(458 mmol)3-三氟甲基-4-溴苯胺、147.6g(916 mmol)间氨基三氟甲苯,126.5g(916 mmol)Rongalite(羟基甲亚磺酸单钠盐二水合物),128.5g(1145 mmol)叔丁醇钾,置换氮气,加入1.65L 二甲基亚砜;加入完毕后,升温至80℃,反应16小时;将反应冷却至25℃,加入水,再用乙酸乙酯萃取3次,有机相合并浓缩,然后使用甲基叔丁基醚(MTBE)重结晶,得到98.3g白色粉末固体2,2’-二(三氟甲基)二氨基联苯(理论量146.7g),收率67%。
1HNMR(CDCl3, 400MHz, ppm):δ7.16(d, J =7.2 Hz,2H), 6.81 (d, J =6.8 Hz,2H) , 6.55(d, J =6.4 Hz,2H), 3.9(d, J =4.0 Hz,4H)。
除上述实施例外,本发明还包括有其他实施方式,凡采用等同变换或者等效替换方式形成的技术方案,均应落入本发明权利要求的保护范围之内。
Claims (9)
2.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:步骤(1)中所述溴化试剂为N-溴代琥珀酰亚胺、溴素、二溴海因中至少一种。
3.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:步骤(1)中所述溴化试剂与间氨基三氟甲苯的摩尔比为0.5-2.0:1。
4.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:所述步骤(1)在溶剂体系中进行,所述溶剂为二氯甲烷、甲苯、有机酰胺类溶剂、有机醚类溶剂、无机酸中至少一种。
5.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:步骤(2)中所述碱性物质为氢氧化钾、氢氧化钠、氢氧化锂、叔丁醇钠、叔丁醇钾、碳酸钠、碳酸钾、碳酸铯、碳酸氢钠、碳酸氢钾、甲醇钠、甲醇钾、二异丙基乙基胺中至少一种。
6.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:步骤(2)中所述碱性物质与3-三氟甲基-4-溴苯胺的摩尔比为0.5-3.0:1。
7.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:所述步骤(2)在溶剂体系中进行,所述溶剂为二甲基亚砜、有机酰胺类溶剂、有机醚类溶剂、有机醇类溶剂、二氯甲烷中至少一种。
8.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:步骤(1)的反应温度为20-30oC,反应时间2-5h。
9.根据权利要求1所述的2,2’-二(三氟甲基)二氨基联苯的合成工艺,其特征在于:步骤(2)的反应温度为75-85oC, 反应时间12-18h。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0298803A1 (fr) * | 1987-06-23 | 1989-01-11 | Rhone-Poulenc Chimie | Procédé de perhalogénoalkylation de dérivés aromatiques |
CN101337895A (zh) * | 2008-08-11 | 2009-01-07 | 武邑天大精细化工高新技术开发中心 | 2,2'-双(三氟甲基)-4,4'-二氨基联苯的制备方法 |
CN107573267A (zh) * | 2017-10-19 | 2018-01-12 | 中国科学院上海有机化学研究所 | 含有三氟甲基的烷基磺酰氟化合物、其制备方法和应用 |
CN111646911A (zh) * | 2020-04-21 | 2020-09-11 | 广东莱佛士制药技术有限公司 | 合成邻氨基苯乙酮的方法 |
-
2022
- 2022-07-11 CN CN202210807782.4A patent/CN115124430B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0298803A1 (fr) * | 1987-06-23 | 1989-01-11 | Rhone-Poulenc Chimie | Procédé de perhalogénoalkylation de dérivés aromatiques |
CN101337895A (zh) * | 2008-08-11 | 2009-01-07 | 武邑天大精细化工高新技术开发中心 | 2,2'-双(三氟甲基)-4,4'-二氨基联苯的制备方法 |
CN107573267A (zh) * | 2017-10-19 | 2018-01-12 | 中国科学院上海有机化学研究所 | 含有三氟甲基的烷基磺酰氟化合物、其制备方法和应用 |
CN111646911A (zh) * | 2020-04-21 | 2020-09-11 | 广东莱佛士制药技术有限公司 | 合成邻氨基苯乙酮的方法 |
Non-Patent Citations (3)
Title |
---|
FAZHI YU ET AL.: "Generation of Aryl Radicals from Aryl Halides: Rongalite-Promoted Transition-Metal-Free Arylation", 《J. ORG. CHEM.》, vol. 84, pages 9946 - 9956 * |
R. ELANCHERAN ET AL.: "Design and development of oxobenzimidazoles as novel androgen receptor antagonists", 《MED CHEM RES》, vol. 25, pages 539 - 552, XP035802929, DOI: 10.1007/s00044-016-1504-3 * |
刘霞 等: "二聚脂肪酸脱色技术研究进展", 《山东化工》, vol. 48, pages 86 - 87 * |
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