JPH0149253B2 - - Google Patents
Info
- Publication number
- JPH0149253B2 JPH0149253B2 JP57120529A JP12052982A JPH0149253B2 JP H0149253 B2 JPH0149253 B2 JP H0149253B2 JP 57120529 A JP57120529 A JP 57120529A JP 12052982 A JP12052982 A JP 12052982A JP H0149253 B2 JPH0149253 B2 JP H0149253B2
- Authority
- JP
- Japan
- Prior art keywords
- chloro
- water
- nitrobenzoic acid
- mmol
- bis
- 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
Links
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 229910052801 chlorine Chemical group 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- -1 fluoromethylphenyl Chemical group 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical class [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 235000011181 potassium carbonates Nutrition 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- GOFURTAJNOZTTO-UHFFFAOYSA-N bis[2-chloro-4-(trifluoromethyl)phenyl] carbonate Chemical compound ClC1=CC(C(F)(F)F)=CC=C1OC(=O)OC1=CC=C(C(F)(F)F)C=C1Cl GOFURTAJNOZTTO-UHFFFAOYSA-N 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- YYQSMJVVERBZPU-UHFFFAOYSA-N 4-chloro-2-ethoxy-1-nitrobenzene Chemical compound CCOC1=CC(Cl)=CC=C1[N+]([O-])=O YYQSMJVVERBZPU-UHFFFAOYSA-N 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ABEUJUYEUCCZQF-UHFFFAOYSA-N 4-chloro-2-methoxy-1-nitrobenzene Chemical compound COC1=CC(Cl)=CC=C1[N+]([O-])=O ABEUJUYEUCCZQF-UHFFFAOYSA-N 0.000 description 2
- CTHFLLKVPMYCPY-UHFFFAOYSA-N 5-chloro-2-nitro-n-propylbenzamide Chemical compound CCCNC(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O CTHFLLKVPMYCPY-UHFFFAOYSA-N 0.000 description 2
- CKCQLHDNVOCCCN-UHFFFAOYSA-N 5-chloro-n-methyl-2-nitrobenzamide Chemical compound CNC(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O CKCQLHDNVOCCCN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000008422 chlorobenzenes Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YXYKZYIDUAHCMZ-UHFFFAOYSA-N n,n-dibutyl-5-chloro-2-nitrobenzamide Chemical compound CCCCN(CCCC)C(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O YXYKZYIDUAHCMZ-UHFFFAOYSA-N 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- BAYGVMXZJBFEMB-UHFFFAOYSA-N 4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1 BAYGVMXZJBFEMB-UHFFFAOYSA-N 0.000 description 1
- CMDZDRYXYNKLNL-UHFFFAOYSA-N 5-chloro-n,n-dimethyl-2-nitrobenzamide Chemical compound CN(C)C(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O CMDZDRYXYNKLNL-UHFFFAOYSA-N 0.000 description 1
- ZHAXSUDLGOYKQV-UHFFFAOYSA-N 5-chloro-n-ethyl-2-nitrobenzamide Chemical compound CCNC(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O ZHAXSUDLGOYKQV-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JFQUVGSOOYKCAH-UHFFFAOYSA-N bis[4-(trifluoromethyl)phenyl] carbonate Chemical compound C1=CC(C(F)(F)F)=CC=C1OC(=O)OC1=CC=C(C(F)(F)F)C=C1 JFQUVGSOOYKCAH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- RICLVXMCOVKPRW-UHFFFAOYSA-N ethyl 5-chloro-2-nitrobenzoate Chemical compound CCOC(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O RICLVXMCOVKPRW-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- VRUZAGKMLZNXMG-UHFFFAOYSA-N n-tert-butyl-5-chloro-2-nitrobenzamide Chemical compound CC(C)(C)NC(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O VRUZAGKMLZNXMG-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- GBSQFXHHPRSEBL-UHFFFAOYSA-N tert-butyl 5-chloro-2-nitrobenzoate Chemical compound CC(C)(C)OC(=O)C1=CC(Cl)=CC=C1[N+]([O-])=O GBSQFXHHPRSEBL-UHFFFAOYSA-N 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
【発明の詳細な説明】
本発明は、ビスフエニルカーボネート類とクロ
ロベンゼン類とからジフエニルエーテル類を製造
する方法に関するものであつて、目的化合物の４
−トリフルオロメチル−4′−ニトロジフエニルエ
ーテル類は除草剤として有用な化合物として知ら
れている。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diphenyl ethers from bisphenyl carbonates and chlorobenzenes.
-Trifluoromethyl-4'-nitrodiphenyl ethers are known as compounds useful as herbicides.
従来から、該ジフエニルエーテル類の製造方法
としては、一般に次の２法が知られている。 Conventionally, the following two methods are generally known as methods for producing diphenyl ethers.
例えば、(i)の方法は特開昭49−236号公報で明
らかにされているが、４−トリフルオロメチルフ
エノールはアルカリの存在下では重合し易く、副
反応を抑制することはむづかしい。そのため目的
物の純度および収率は著しく低い。 For example, method (i) is disclosed in JP-A-49-236, but 4-trifluoromethylphenol is easily polymerized in the presence of an alkali, and it is difficult to suppress side reactions. Therefore, the purity and yield of the target product are extremely low.
また(ii)の方法は、Journal of Agricultural
and Food chemistry第26巻、285頁（1978年）
に記載されており、更にエステル化あるいはアミ
ド化により種々の誘導体が得られる。しかしこの
方法は、ニトロ化反応工程で目的物以外の異性体
を多量に副生するなど、工業化に際し不都合な問
題点が多く、早急に有利な製造方法の確立が望ま
れている。 Also, method (ii) is published in the Journal of Agricultural
and Food chemistry Vol. 26, p. 285 (1978)
and various derivatives can be obtained by further esterification or amidation. However, this method has many problems that are inconvenient for industrialization, such as the production of a large amount of isomers other than the target product in the nitration reaction step, and there is an urgent need to establish an advantageous production method.
本発明者等は、このような問題点を克服すべく
鋭意研究を重ねた結果、ビスジフエニルカーボネ
ート類とクロロベンゼン類とから高純度のジフエ
ニルエーテル類を工業的規模で効率的にかつ高収
率で製造する新規な方法を見出し、本発明を完成
するに至つた。 As a result of extensive research to overcome these problems, the present inventors have succeeded in producing high-purity diphenyl ethers from bisdiphenyl carbonates and chlorobenzenes efficiently and in high yields on an industrial scale. We have discovered a new method for manufacturing at a high rate of production, and have completed the present invention.
すなわち、本発明は、一般式
（式中、Ｘは水素原子または塩素原子を示す。）
で表わされるビス−４−トリフルオロメチルフエ
ニルカーボネート類と、
一般式
〔式中、Ｙは水素原子、−OR、−COOR、−
CONHR、−CON（Ｒ）2（Ｒは低級アルキル基を示
す。）基を示す。〕で表わされる４−クロロニトロ
ベンゼン類とを不活性有機溶媒中、アルカリ金属
炭酸塩または重炭酸塩の存在下に反応させること
を特徴とする一般式、
（ＸおよびＹは一般式(1)および(2)と同一の意味を
有する。）で表わされる４−トリフルオロメチル
−4′−ニトロジフエニルエーテル類の製造法であ
る。 That is, the present invention provides the general formula (In the formula, X represents a hydrogen atom or a chlorine atom.)
Bis-4-trifluoromethylphenyl carbonates represented by the general formula [In the formula, Y is a hydrogen atom, -OR, -COOR, -
CONHR, -CON(R) 2 (R represents a lower alkyl group) group. A general formula characterized by reacting 4-chloronitrobenzenes represented by ] in an inert organic solvent in the presence of an alkali metal carbonate or bicarbonate, (X and Y have the same meanings as in general formulas (1) and (2).) This is a method for producing 4-trifluoromethyl-4'-nitrodiphenyl ethers.
本発明方法に使用する一般式(1)で表わされるビ
ス−４−トリフルオロメチルフエニルカーボネー
ト類としては、例えばビス−４−トリフルオロメ
チルフエニルカーボネート、ビス−（２−クロロ
−４−トリフルオロメチルフエニル）カーボネー
トが挙げられる。 Examples of bis-4-trifluoromethylphenyl carbonates represented by general formula (1) used in the method of the present invention include bis-4-trifluoromethylphenyl carbonate, bis-(2-chloro-4-trifluorocarbonate), and bis-(2-chloro-4-trifluoromethylphenyl carbonate). Examples include fluoromethylphenyl) carbonate.
また一般式(2)で表わされる４−クロロニトロベ
ンゼン類の置換基Ｙの低級アルキル基を示すＲは
１〜４までの炭素原子を有するものである。 Further, R representing the lower alkyl group of the substituent Y of the 4-chloronitrobenzene represented by the general formula (2) has 1 to 4 carbon atoms.
具体的には、
４−クロロニトロベンゼン、
３−メトキシ−４−ニトロクロロベンゼン、
３−エトキシ−４−ニトロクロロベンゼン、
４−ニトロ−３−プロピルオキシクロロベンゼ
ン、
３−ｉ−プロピルオキシ−４−ニトロクロロベ
ンゼン、
３−ブトキシ−４−ニトロクロロベンゼン、
３−ｉ−ブトキシ−４−ニトロクロロベンゼ
ン、
３−ｓ−ブトキシ−４−ニトロクロロベンゼ
ン、
３−ｔ−ブトキシ−４−ニトロクロロベンゼ
ン、
５−クロロ−２−ニトロ安息香酸メチルエステ
ル、
５−クロロ−２−ニトロ安息香酸エチルエステ
ル、
５−クロロ−２−ニトロ安息香酸プロピルエス
テル、
５−クロロ−２−ニトロ安息香酸−ｉ−プロピ
ルエステル、
５−クロロ−２−ニトロ安息香酸ブチルエステ
ル、
５−クロロ−２−ニトロ安息香酸−ｉ−ブチル
エステル、
５−クロロ−２−ニトロ安息香酸−ｓ−ブチル
エステル、
５−クロロ−２−ニトロ安息香酸−ｔ−ブチル
エステル、
Ｎ−メチル−５−クロロ−２−ニトロ安息香酸
アミド、
Ｎ−エチル−５−クロロ−２−ニトロ安息香酸
アミド、
Ｎ−プロピル−５−クロロ−２−ニトロ安息香
酸アミド、
Ｎ−ｉ−プロピル−５−クロロ−２−ニトロ安
息香酸アミド、
Ｎ−ブチル−５−クロロ−２−ニトロ安息香酸
アミド、
Ｎ−ｉ−ブチル−５−クロロ−２−ニトロ安息
香酸アミド、
Ｎ−ｓ−ブチル−５−クロロ−２−ニトロ安息
香酸アミド、
Ｎ−ｔ−ブチル−５−クロロ−２−ニトロ安息
香酸アミド、
Ｎ，Ｎ−ジメチル−５−クロロ−２−ニトロ安
息香酸アミド、
Ｎ，Ｎ−ジエチル−５−クロロ−２−ニトロ安
息香酸アミド、
Ｎ，Ｎ−ジプロピル−５−クロロ−２−ニトロ
安息香酸アミド、
Ｎ，Ｎ−ジ−ｉ−プロピル−５−クロロ−２−
ニトロ安息香酸アミド、
Ｎ，Ｎ−ジブチル−５−クロロ−２−ニトロ安
息香酸アミド、
Ｎ，Ｎ−ジ−ｉ−ブチル−５−クロロ−２−ニ
トロ安息香酸アミド、
Ｎ，Ｎ−ジ−ｓ−ブチル−５−クロロ−２−ニ
トロ安息香酸アミド、
Ｎ，Ｎ−ジ−ｔ−ブチル−５−クロロ−２−ニ
トロ安息香酸アミド等を例示することができる。 Specifically, 4-chloronitrobenzene, 3-methoxy-4-nitrochlorobenzene, 3-ethoxy-4-nitrochlorobenzene, 4-nitro-3-propyloxychlorobenzene, 3-i-propyloxy-4-nitrochlorobenzene, 3-butoxy-4-nitrochlorobenzene, 3-i-butoxy-4-nitrochlorobenzene, 3-s-butoxy-4-nitrochlorobenzene, 3-t-butoxy-4-nitrochlorobenzene, 5-chloro-2-nitrobenzoin acid methyl ester, 5-chloro-2-nitrobenzoic acid ethyl ester, 5-chloro-2-nitrobenzoic acid propyl ester, 5-chloro-2-nitrobenzoic acid-i-propyl ester, 5-chloro-2-nitro Benzoic acid butyl ester, 5-chloro-2-nitrobenzoic acid-i-butyl ester, 5-chloro-2-nitrobenzoic acid-s-butyl ester, 5-chloro-2-nitrobenzoic acid-t-butyl ester, N-methyl-5-chloro-2-nitrobenzoic acid amide, N-ethyl-5-chloro-2-nitrobenzoic acid amide, N-propyl-5-chloro-2-nitrobenzoic acid amide, N-i-propyl -5-chloro-2-nitrobenzoic acid amide, N-butyl-5-chloro-2-nitrobenzoic acid amide, N-i-butyl-5-chloro-2-nitrobenzoic acid amide, N-s-butyl- 5-chloro-2-nitrobenzoic acid amide, N-t-butyl-5-chloro-2-nitrobenzoic acid amide, N,N-dimethyl-5-chloro-2-nitrobenzoic acid amide, N,N-diethyl -5-chloro-2-nitrobenzoic acid amide, N,N-dipropyl-5-chloro-2-nitrobenzoic acid amide, N,N-di-i-propyl-5-chloro-2-
Nitrobenzoic acid amide, N,N-dibutyl-5-chloro-2-nitrobenzoic acid amide, N,N-di-i-butyl-5-chloro-2-nitrobenzoic acid amide, N,N-di-s Examples include -butyl-5-chloro-2-nitrobenzoic acid amide, N,N-di-t-butyl-5-chloro-2-nitrobenzoic acid amide, and the like.
これらのビス−４−トリフルオロメチルフエニ
ルカーボネート類および４−クロロニトロベンゼ
ン類は公知の方法により容易に合成することがで
きる。 These bis-4-trifluoromethylphenyl carbonates and 4-chloronitrobenzenes can be easily synthesized by known methods.
本発明の方法に使用する不活性有機溶媒として
は、反応温度の維持、反応試剤の活性化等を加味
してジメチルホルムアミド、ジメチルスルホキシ
ド、スルホラン、ジメチルアセトアミド等が好適
である。 As the inert organic solvent used in the method of the present invention, dimethylformamide, dimethylsulfoxide, sulfolane, dimethylacetamide, etc. are suitable, taking into consideration the maintenance of reaction temperature, activation of reaction reagents, etc.
使用する溶媒量は４−クロロニトロベンゼン類
に対して２〜20重量倍が適当であり、好ましくは
３〜10倍量である。 The amount of solvent used is suitably 2 to 20 times the weight of the 4-chloronitrobenzenes, preferably 3 to 10 times the amount by weight.
アルカリ金属化合物としては、炭酸カリウム、
炭酸ナトリウム、炭酸水素カリウムおよび炭酸水
素ナトリウムが用いられるが、特に炭酸カリウム
が好適である。アルカリ金属化合物の使用量は４
−クロロニトロベンゼン類１モルに対し、1.0〜
5.0モルの範囲が適当であり、好ましくは1.0〜2.0
モルである。 As alkali metal compounds, potassium carbonate,
Sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate are used, with potassium carbonate being particularly preferred. The amount of alkali metal compound used is 4
-1.0 to 1 mole of chloronitrobenzenes
A range of 5.0 mol is appropriate, preferably 1.0 to 2.0
It is a mole.
４−クロロニトロベンゼン類とビス−４−トリ
フルオロメチルフエニルカーボネート類との使用
割合は、４−クロロニトロベンゼン類１モルに対
し、ビス−４−トリフルオロメチルフエニルカー
ボネート類0.5〜0.7モルが適当であり、好ましく
は0.50〜0.60モルである。 The appropriate ratio of 4-chloronitrobenzenes and bis-4-trifluoromethylphenyl carbonates to be used is 0.5 to 0.7 moles of bis-4-trifluoromethylphenyl carbonates per 1 mole of 4-chloronitrobenzenes. and preferably 0.50 to 0.60 mol.
４−クロロニトロベンゼン類とビス−４−トリ
フルオロメチルフエニルカーボネート類との反応
は、水分の存在を嫌うので反応系の水はできる限
り除去する必要がある。水分の除去の方法として
は、不活性有機溶媒およびアルカリ金属化合物を
反応器に仕込んだ後、ベンゼン、トルエン等の水
と共沸する溶媒を加えて共沸蒸留するのがよい。
次いで、過剰の共沸溶媒を留去した後、４−クロ
ロニトロベンゼン類とビス−４−トリフルオロメ
チルフエニルカーボネート類を仕込み反応を行な
う。あるいはベンゼン、トルエンを留去せず、反
応を進行させながら水を留去させることもでき
る。 The reaction between 4-chloronitrobenzenes and bis-4-trifluoromethylphenyl carbonates dislikes the presence of water, so it is necessary to remove as much water as possible from the reaction system. As a method for removing water, it is preferable to charge an inert organic solvent and an alkali metal compound into a reactor, then add a solvent that is azeotropic with water, such as benzene or toluene, and perform azeotropic distillation.
Next, after distilling off the excess azeotropic solvent, 4-chloronitrobenzenes and bis-4-trifluoromethylphenyl carbonates are charged and reacted. Alternatively, water may be distilled off while the reaction proceeds without benzene or toluene being distilled off.
反応温度は100〜150℃の範囲が好適である。さ
らに好ましくは100〜125℃である。100℃以下で
はエーテル化の反応速度が遅く、反応完結には長
時間を要する。150℃以上では副生成物の生成割
合が多くなり、収率、純度ともに低くなる。 The reaction temperature is preferably in the range of 100 to 150°C. More preferably, the temperature is 100 to 125°C. Below 100°C, the etherification reaction rate is slow and it takes a long time to complete the reaction. At temperatures above 150°C, the proportion of by-products produced increases, resulting in low yield and purity.
反応時間は、主に反応温度、使用される試薬の
種類により異なるが10〜40時間程度である。 The reaction time varies mainly depending on the reaction temperature and the type of reagent used, but is approximately 10 to 40 hours.
４−クロロニトロベンゼン類とビス−４−トリ
フルオロメチルフエニルカーボネート類との反応
は、酸化性物質の存在が副生成物の生成割合を増
加させるので、反応は窒素、ヘリウム、アルゴン
等の不活性気流中にて行なうのがよい。 In the reaction between 4-chloronitrobenzenes and bis-4-trifluoromethylphenyl carbonates, the presence of oxidizing substances increases the rate of by-product formation, so the reaction is carried out using inert gases such as nitrogen, helium, and argon. It is best to do this in a stream of air.
反応終了後、必要により減圧蒸留に付し溶剤を
回収し、残留物を水の中へ注ぐことにより目的の
ジフエニルエーテル体を分離することができる。
あるいは水と、水に不溶なベンゼン、トルエン等
の溶剤を用い、抽出によつてジフエニルエーテル
体を分離してもよい。 After the reaction is completed, the desired diphenyl ether compound can be separated by subjecting it to distillation under reduced pressure to recover the solvent and pouring the residue into water, if necessary.
Alternatively, the diphenyl ether compound may be separated by extraction using water and a water-insoluble solvent such as benzene or toluene.
本発明の方法によれば高純度のジフエニルエー
テル体が高収率で得られるので、通常は粗生成物
をそのまま目的とする用途に利用することができ
る。 According to the method of the present invention, a highly purified diphenyl ether compound can be obtained in a high yield, so that the crude product can usually be used as is for the intended purpose.
以下、本発明を実施例によつて具体的に説明す
る。 Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例 １
ジメチルホルムアミド200ｇ中に炭酸カリウム
28.0ｇ（202ミリモル）およびベンゼン150ｇを加
え、水分離器および窒素導入管を付し、溶剤に溶
解している空気および反応器内の空気を窒素置換
した後、窒素雰囲気下で反応系内の水を共沸留去
した。さらにベンゼンを留去後、ビス−（２−ク
ロロ−４−トリフルオロメチルフエニル）カーボ
ネート24ｇ（57ミリモル）および５−クロロ−２
−ニトロ安息香酸−ｉ−プロピルエステル25ｇ
（103ミリモル）を添加し、窒素気流中110℃にて
14時間撹拌した。冷却後、反応混合物を２％水酸
化ナトリウム水溶液の中へ注ぎ15分程室温にて撹
拌した後、不溶物を別した。水洗後乾燥し37.5
ｇの５−〔２−クロロ−４−（トリフルオロメチ
ル）フエノキシ〕−２−ニトロ安息香酸−ｉ−プ
ロピルエステルを収率90.1％で得た。ガスクロマ
トグラフイーによる純度は97.8％、融点53〜55℃
であつた。Example 1 Potassium carbonate in 200g of dimethylformamide
Add 28.0 g (202 mmol) and 150 g of benzene, attach a water separator and a nitrogen inlet pipe, replace the air dissolved in the solvent and the air in the reactor with nitrogen, and then drain the reaction system in a nitrogen atmosphere. Water was distilled off azeotropically. Furthermore, after distilling off benzene, 24 g (57 mmol) of bis-(2-chloro-4-trifluoromethylphenyl) carbonate and 5-chloro-2
-Nitrobenzoic acid-i-propyl ester 25g
(103 mmol) was added at 110℃ in a nitrogen stream.
Stirred for 14 hours. After cooling, the reaction mixture was poured into a 2% aqueous sodium hydroxide solution, stirred at room temperature for about 15 minutes, and then insoluble materials were separated. Dry after washing with water 37.5
g of 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid-i-propyl ester was obtained in a yield of 90.1%. Purity by gas chromatography is 97.8%, melting point 53-55℃
It was hot.
実施例 ２
ジメチルホルムアミド70ｇ中に炭酸カリウム
14.5ｇ（105ミリモル）およびベンゼン30ｇを加
え、水分離器および窒素導入管を付し、窒素気流
中、反応系内の水を共沸留去した。ビス−（２−
クロロ−４−トリフルオロメチルフエニル）カー
ボネート15.4ｇ（37ミリモル）およびＮ−メチル
−５−クロロ−２−ニトロ安息香酸アミド15.0ｇ
（70ミリモル）を添加し窒素気流中、ベンゼンに
よる共沸脱水下、120℃にて25時間撹拌した。冷
却後反応混合物を２％水酸化ナトリウム水溶液の
中へ注ぎ、ベンゼンを用いて抽出した。ベンゼン
層を水洗後、無水硫酸ナトリウムで脱水し溶媒を
減圧蒸留除去することにより23.9ｇのＮ−メチル
−５−〔２−クロロ−４−（トリフルオロメチル）
フエノキシ〕−２−ニトロ安息香酸アミドを収率
91.2％で得た。（純度97.4％、融点136〜139℃）
実施例 ３
ジメチルスルホキシド300ｇ中に炭酸カリウム
37ｇ（268ミリモル）およびベンゼン50ｇを加え、
水分離器および窒素導入管を付し、窒素気流中、
反応系内の水を共沸留去した。さらにベンゼンを
留去後、ビス−（４−トリフルオロメチルフエニ
ル）カーボネート26.3ｇ（75ミリモル）および３
−エトキシ−４−ニトロクロロベンゼン30.2ｇ
（150ミリモル）を添加し窒素気流中、120℃で11
時間撹拌した。冷却後、反応混合物を水の中へ注
ぎ不溶物を別した。水洗後乾燥し43.1ｇの３−
エトキシ−４−ニトロ−4′−トリフルオロメチル
ジフエニルエーテルを収率87.8％で得た。（純度
98.1％、融点72〜74℃）
実施例 ４
ジメチルホルムアミド35ｇ中に炭酸カリウム10
ｇ（72ミリモル）およびベンゼン30ｇを加え、水
分離器および窒素導入管を付し、窒素気流中、反
応系内の水を共沸留去した。さらにベンゼンを留
去後、ビス−（２−クロロ−４−トリフルオロメ
チルフエニル）カーボネート9.2ｇ（22ミリモル）
およびｐ−ニトロクロロベンゼン6.3ｇ（40ミリ
モル）を添加し、窒素気流中、100℃にて28時間
撹拌した。反応終了後、減圧下ジメチルホルムア
ミドを留去し、残留物を水の中へ加え、10分程撹
拌した。不溶物を別水洗後、乾燥し11.2ｇの２
−クロロ−４−トリフルオロメチル−4′−ニトロ
ジフエニルエーテルを収率88.2％で得た。（純度
97.6％、融点68〜71℃）
実施例 ５
ジメチルホルムアミド40ｇ中に炭酸カリウム17
ｇ（123ミリモル）およびベンゼン30ｇを加え、
水分離器および窒素導入管を付し、窒素気流中、
反応系内の水を共沸留去した。さらにベンゼンを
留去後、ビス−（２−クロロ−４−トリフルオロ
メチルフエニル）カーボネート16.8ｇ（40ミリモ
ル）および３−エトキシ−４−ニトロクロロベン
ゼン14.7ｇ（73ミリモル）を仕込み110℃で25時
間撹拌した。反応終了後反応混合物を水の中へ注
ぎ、不溶物を別水洗後乾燥し、23.1ｇの２−ク
ロロ−４−トリフルオロメチル−3′−エトキシ−
4′−ニトロジフエニルエーテルを収率87.5％で得
た。（純度98.2％、融点82〜84℃）
実施例 ６
ジメチルホルムアミド110ｇ中に炭酸水素カリ
ウム14ｇ（140ミリモル）およびベンゼン40ｇを
加え、水分離器および窒素導入管を付し、窒素気
流中、反応系内の水を共沸留去した。さらにベン
ゼンを留去後、ビス−（２−クロロ−４−トリフ
ルオロメチルフエニル）カーボネート20.6ｇ（49
ミリモル）および３−メトキシ−４−ニトロクロ
ロベンゼン15.4ｇ（82ミリモル）を仕込み、125
℃で26時間撹拌した。反応終了後、反応混合物を
２％水酸化ナトリウム水溶液の中へ注ぎ、不溶物
を別水洗後、乾燥し24.1ｇの２−クロロ−４−
トリフルオロメチル−3′−メトキシ−4′−ニトロ
ジフエニルエーテルを収率84.6％で得た。（純度
96.4％、融点98〜101℃）
実施例 ７
ジメチルホルムアミド50ｇに炭酸ナトリウム15
ｇ（141ミリモル）およびトルエン30ｇを加え、
水分離器および窒素導入管を付し、窒素気流中、
反応系内の水を共沸留去した。さらにトルエンを
留去後、ビス−（２−クロロ−４−トリフルオロ
メチルフエニル）カーボネート9.0ｇ（21ミリモ
ル）およびｐ−ニトロクロロベンゼン5.7ｇ（36
ミリモル）を加え125℃で24時間撹拌した。反応
終了後、溶媒を減圧留去し、残留物をトルエンを
用いて抽出した。トルエン層を５％水酸化ナトリ
ウム水溶液で洗浄後、硫酸ナトリウムで脱水しト
ルエンを留去することにより9.5ｇの２−クロロ
−４−トリフルオロメチル−4′−ニトロジフエニ
ルエーテルを収率83.3％で得た。（純度96.2％、
融点67〜70℃）Example 2 Potassium carbonate in 70 g of dimethylformamide
14.5 g (105 mmol) and 30 g of benzene were added, a water separator and a nitrogen inlet tube were attached, and water in the reaction system was azeotropically distilled off in a nitrogen stream. Bis-(2-
15.4 g (37 mmol) of chloro-4-trifluoromethylphenyl)carbonate and 15.0 g of N-methyl-5-chloro-2-nitrobenzoic acid amide
(70 mmol) was added, and the mixture was stirred at 120°C for 25 hours under azeotropic dehydration with benzene in a nitrogen stream. After cooling, the reaction mixture was poured into a 2% aqueous sodium hydroxide solution and extracted using benzene. After washing the benzene layer with water, it was dehydrated with anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure to obtain 23.9 g of N-methyl-5-[2-chloro-4-(trifluoromethyl)].
Yield of phenoxy]-2-nitrobenzoic acid amide
Obtained with 91.2%. (Purity 97.4%, melting point 136-139℃) Example 3 Potassium carbonate in 300g of dimethyl sulfoxide
Add 37 g (268 mmol) and 50 g of benzene,
Equipped with a water separator and nitrogen inlet pipe, in a nitrogen stream,
Water in the reaction system was azeotropically distilled off. Furthermore, after distilling off benzene, 26.3 g (75 mmol) of bis-(4-trifluoromethylphenyl) carbonate and 3
-Ethoxy-4-nitrochlorobenzene 30.2g
(150 mmol) at 120℃ in a nitrogen stream for 11 hours.
Stir for hours. After cooling, the reaction mixture was poured into water to separate insoluble matter. After washing with water and drying, 43.1g of 3-
Ethoxy-4-nitro-4'-trifluoromethyl diphenyl ether was obtained in a yield of 87.8%. (purity
98.1%, melting point 72-74℃) Example 4 Potassium carbonate 10% in 35g dimethylformamide
g (72 mmol) and 30 g of benzene were added, a water separator and a nitrogen inlet tube were attached, and water in the reaction system was azeotropically distilled off in a nitrogen stream. Furthermore, after distilling off benzene, 9.2 g (22 mmol) of bis-(2-chloro-4-trifluoromethylphenyl) carbonate
and 6.3 g (40 mmol) of p-nitrochlorobenzene were added thereto, and the mixture was stirred at 100° C. for 28 hours in a nitrogen stream. After the reaction was completed, dimethylformamide was distilled off under reduced pressure, and the residue was added to water and stirred for about 10 minutes. After washing the insoluble matter separately with water, dry it and remove 11.2 g of 2
-Chloro-4-trifluoromethyl-4'-nitrodiphenyl ether was obtained in a yield of 88.2%. (purity
97.6%, melting point 68-71℃) Example 5 Potassium carbonate 17 in 40g dimethylformamide
g (123 mmol) and 30 g of benzene,
Equipped with a water separator and nitrogen inlet pipe, in a nitrogen stream,
Water in the reaction system was azeotropically distilled off. After distilling off the benzene, 16.8 g (40 mmol) of bis-(2-chloro-4-trifluoromethylphenyl) carbonate and 14.7 g (73 mmol) of 3-ethoxy-4-nitrochlorobenzene were charged and heated at 110℃ for 25 hours. Stir for hours. After the reaction was completed, the reaction mixture was poured into water, the insoluble matter was washed with water and dried, and 23.1 g of 2-chloro-4-trifluoromethyl-3'-ethoxy-
4'-nitrodiphenyl ether was obtained with a yield of 87.5%. (Purity 98.2%, melting point 82-84°C) Example 6 14 g (140 mmol) of potassium hydrogen carbonate and 40 g of benzene were added to 110 g of dimethylformamide, and a water separator and nitrogen inlet pipe were attached, and the reaction system was heated in a nitrogen stream. The water inside was distilled off azeotropically. Furthermore, after distilling off benzene, 20.6 g of bis-(2-chloro-4-trifluoromethylphenyl) carbonate (49
125 mmol) and 15.4 g (82 mmol) of 3-methoxy-4-nitrochlorobenzene.
Stirred at ℃ for 26 hours. After the reaction was completed, the reaction mixture was poured into a 2% aqueous sodium hydroxide solution, the insoluble matter was washed separately with water, and then dried to give 24.1 g of 2-chloro-4-
Trifluoromethyl-3'-methoxy-4'-nitrodiphenyl ether was obtained in a yield of 84.6%. (purity
96.4%, melting point 98-101℃) Example 7 50g of dimethylformamide and 15% of sodium carbonate
g (141 mmol) and 30 g of toluene,
Equipped with a water separator and nitrogen inlet pipe, in a nitrogen stream,
Water in the reaction system was azeotropically distilled off. After further distilling off toluene, 9.0 g (21 mmol) of bis-(2-chloro-4-trifluoromethylphenyl) carbonate and 5.7 g (36 mmol) of p-nitrochlorobenzene were added.
mmol) and stirred at 125°C for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was extracted using toluene. After washing the toluene layer with a 5% aqueous sodium hydroxide solution, the toluene layer was dehydrated with sodium sulfate and the toluene was distilled off to obtain 9.5 g of 2-chloro-4-trifluoromethyl-4'-nitrodiphenyl ether in a yield of 83.3%. I got it from (Purity 96.2%,
Melting point 67-70℃)
Claims (1)
で表わされるビス−４−トリフルオロメチルフエ
ニルカーボネート類と、 一般式 〔式中、Ｙは水素原子、−OR、−COOR、−
CONHR、−CON（Ｒ）2（Ｒは低級アルキル基を示
す）基を示す。〕で表わされる４−クロロニトロ
ベンゼン類とを不活性有機溶媒中、アルカリ金属
炭酸塩または重炭酸塩の存在下に反応させること
を特徴とする。 一般式 （ＸおよびＹは一般式(1)および(2)と同一の意味を
有する。）で表わされる、４−トリフルオロメチ
ル−4′−ニトロジフエニルエーテル類の製造法。[Claims] 1. General formula (In the formula, X represents a hydrogen atom or a chlorine atom.)
Bis-4-trifluoromethylphenyl carbonates represented by the general formula [In the formula, Y is a hydrogen atom, -OR, -COOR, -
CONHR, -CON(R) 2 (R represents a lower alkyl group) group. ] in an inert organic solvent in the presence of an alkali metal carbonate or bicarbonate. general formula (X and Y have the same meanings as in general formulas (1) and (2).) A method for producing 4-trifluoromethyl-4'-nitrodiphenyl ethers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57120529A JPS5913749A (en) | 1982-07-13 | 1982-07-13 | Preparation of 4-trifluoromethyl-4'-nitrodiphenyl ether compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57120529A JPS5913749A (en) | 1982-07-13 | 1982-07-13 | Preparation of 4-trifluoromethyl-4'-nitrodiphenyl ether compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5913749A JPS5913749A (en) | 1984-01-24 |
| JPH0149253B2 true JPH0149253B2 (en) | 1989-10-24 |
Family
ID=14788524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57120529A Granted JPS5913749A (en) | 1982-07-13 | 1982-07-13 | Preparation of 4-trifluoromethyl-4'-nitrodiphenyl ether compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5913749A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2605668B2 (en) * | 1986-11-28 | 1997-04-30 | カシオ計算機株式会社 | Electronic string instrument |
| JPS63155194U (en) * | 1987-03-30 | 1988-10-12 | ||
| JP2679725B2 (en) * | 1987-03-24 | 1997-11-19 | カシオ計算機株式会社 | Electronic string instrument |
| JPS63191397U (en) * | 1987-05-27 | 1988-12-09 | ||
| JPS642297U (en) * | 1987-06-22 | 1989-01-09 | ||
| JPS63137295A (en) * | 1987-09-24 | 1988-06-09 | カシオ計算機株式会社 | Electronic stringed instrument |
| JPH0493995A (en) * | 1990-08-07 | 1992-03-26 | Yamaha Corp | Electronic musical instrument |
-
1982
- 1982-07-13 JP JP57120529A patent/JPS5913749A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5913749A (en) | 1984-01-24 |
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