JPH01163157A - Production of fluorinated nitrobenzenes - Google Patents
Production of fluorinated nitrobenzenesInfo
- Publication number
- JPH01163157A JPH01163157A JP62321047A JP32104787A JPH01163157A JP H01163157 A JPH01163157 A JP H01163157A JP 62321047 A JP62321047 A JP 62321047A JP 32104787 A JP32104787 A JP 32104787A JP H01163157 A JPH01163157 A JP H01163157A
- Authority
- JP
- Japan
- Prior art keywords
- carbonate
- formula
- expressed
- fluorinated
- group
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 150000005181 nitrobenzenes Chemical class 0.000 title claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003513 alkali Substances 0.000 claims description 3
- 125000006350 alkyl thio alkyl group Chemical group 0.000 claims description 3
- 150000005323 carbonate salts Chemical class 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229940100198 alkylating agent Drugs 0.000 abstract description 3
- 239000002168 alkylating agent Substances 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- JPNBVWIRDQVGAC-UHFFFAOYSA-N (2-nitrophenyl) hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=C1[N+]([O-])=O JPNBVWIRDQVGAC-UHFFFAOYSA-N 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000000802 nitrating effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HRZUDEPOLKJQDY-UHFFFAOYSA-N bis(2-chloro-4-fluoro-5-nitrophenyl) carbonate Chemical compound C1=C(F)C([N+](=O)[O-])=CC(OC(=O)OC=2C(=CC(F)=C(C=2)[N+]([O-])=O)Cl)=C1Cl HRZUDEPOLKJQDY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- YMHXXJJTAGKFBA-UHFFFAOYSA-N 1-bromo-2-chloropropane Chemical compound CC(Cl)CBr YMHXXJJTAGKFBA-UHFFFAOYSA-N 0.000 description 1
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 1
- HPEUGDZNJLIBFP-UHFFFAOYSA-N 1-bromo-2-methylsulfanylethane Chemical compound CSCCBr HPEUGDZNJLIBFP-UHFFFAOYSA-N 0.000 description 1
- MYFKLQFBFSHBPA-UHFFFAOYSA-N 1-chloro-2-methylsulfanylethane Chemical compound CSCCCl MYFKLQFBFSHBPA-UHFFFAOYSA-N 0.000 description 1
- ANYDHFJLAAOZED-UHFFFAOYSA-N 1-chloro-4-nitro-2,5-di(propan-2-yloxy)benzene Chemical compound CC(C)OC1=CC([N+]([O-])=O)=C(OC(C)C)C=C1Cl ANYDHFJLAAOZED-UHFFFAOYSA-N 0.000 description 1
- JBOLLKBDFUZSRY-UHFFFAOYSA-N 1-chloro-5-fluoro-4-nitro-2-prop-2-ynoxybenzene Chemical compound [O-][N+](=O)C1=CC(OCC#C)=C(Cl)C=C1F JBOLLKBDFUZSRY-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- NAWVMCKMQMJQMF-UHFFFAOYSA-N 2-chloro-4-fluoro-5-nitrophenol Chemical compound OC1=CC([N+]([O-])=O)=C(F)C=C1Cl NAWVMCKMQMJQMF-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ULAUBQTVYAVTFT-UHFFFAOYSA-N dinitro carbonate Chemical compound [O-][N+](=O)OC(=O)O[N+]([O-])=O ULAUBQTVYAVTFT-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- OKXGHXHZNCJMSV-UHFFFAOYSA-N nitro phenyl carbonate Chemical group [O-][N+](=O)OC(=O)OC1=CC=CC=C1 OKXGHXHZNCJMSV-UHFFFAOYSA-N 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- LJZPPWWHKPGCHS-UHFFFAOYSA-N propargyl chloride Chemical compound ClCC#C LJZPPWWHKPGCHS-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の利用分野］
本発明は、農薬、医薬、染料、色素等の中間体として有
用な化合物であるフッ素化ニトロベンゼン類の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method for producing fluorinated nitrobenzenes, which are compounds useful as intermediates for agricultural chemicals, medicines, dyes, pigments, and the like.
［従来技術とその問題点］
フッ素原子を有するニトロフェノール類のフェノール基
をアルキル化する方法としては、一般に含水アルコール
中、該ニトロフェノールのアルカリ塩とハロゲン化アル
キル類と反応せしめるか、炭酸アルカリ塩の存在下に該
ニトロフェノールとハロゲン化アルキル類とを反応させ
る方法が考えられる。この様な方法に依る問題点は、フ
ッ素原子が脱離することであり、目的物の収量と純度を
低下させ精製を困難にすることはもとより、例えばガラ
ス製の反応容器や装置を腐食させる危険を伴うことが普
通である。[Prior art and its problems] Generally, as a method for alkylating the phenol group of nitrophenols having a fluorine atom, an alkali salt of the nitrophenol is reacted with an alkyl halide in aqueous alcohol, or an alkali carbonate salt is reacted with an alkali salt of the nitrophenol and an alkyl halide. A possible method is to react the nitrophenol with an alkyl halide in the presence of. The problem with such a method is that fluorine atoms are eliminated, which not only reduces the yield and purity of the target product and makes purification difficult, but also poses a risk of corroding glass reaction vessels and equipment. Usually accompanied by
［問題点を解決する為の手段］
か＼る観点から、いかに選択性良く目的物を得るかを鋭
意検討した結果、一般式（１）（式中Ｒは、水素原子、
ハロゲン原子のいずれかを表す）で表されるニトロフェ
ニル−カーボネートを、非水溶媒中で炭酸アルカリ塩の
存在下にＲ’ Ｘ （Ｒ’は、Ｃ１〜Ｃ６のアルキル基
、シクロアルキル基、Ｃ３〜Ｃ６のアルケニル基、Ｃ３
〜ＣＧのアルキニル基、Ｃ１〜Ｃ６のハロゲン化アルキ
ル基、０３〜Ｃ６のハロゲン化アルケニル基、Ｃ２〜Ｃ
６のアルキルチオアルキル基のいずれかを表し、Ｘはハ
ロゲン原子を表す）で示されるアルキル化剤と反応させ
ることにより、事実上副反応を完全に阻止し得ることが
分り、本発明を完成するに至った。[Means for solving the problem] From these viewpoints, as a result of intensive study on how to obtain the desired product with good selectivity, we found that the general formula (1) (wherein R is a hydrogen atom,
nitrophenyl carbonate represented by R' ~C6 alkenyl group, C3
~CG alkynyl group, C1-C6 halogenated alkyl group, 03-C6 halogenated alkenyl group, C2-C
It has been found that by reacting with an alkylating agent represented by the following alkylthioalkyl group (X represents any of the alkylthioalkyl groups of No. 6 and X represents a halogen atom), side reactions can be virtually completely inhibited, and in order to complete the present invention. It's arrived.
更に詳細に説明すれば、原料カーボネート類は出来る限
り乾燥し、水分を含まないものが望ましい。用いる非水
溶媒としては反応速度を高める為に非プロトン性の極性
溶媒が望ましく、例えば、アセトン、メチルエチルケト
ン、アセトニトリル、プロピオニトリル、テトラヒドロ
フラン、ジメチルホルムアミド、ジメチルスルホキサイ
ド等を単独で或いは混合して用いることが出来る。炭酸
アルカリ塩としては、例えば、炭酸ナトリウム、炭酸カ
リウム、炭酸カルシウム、炭酸バリウム等が用いられる
が、炭酸ナトリウム或いは炭酸カリウムが適しており、
これらのいずれかの無水物を、該ニトロカーボネートに
対して２乃至３モル以上用いることが望ましい。アルキ
ル化剤としては、０１〜ＣＧのハロゲン化アルキル例え
ば、ヨウ化メチル、臭化エチル、臭化イソプロピル、臭
化イソブチル、塩化ヘキシル、塩化シクロヘキシル等が
あげられ、０３〜ＣＧのハロゲン化アルケン、例えば、
塩化アリル、１−クロロ−ブテン−２，１−クロロ−３
−メチル−ブテン−２等があげられ、０３〜Ｃ６のハロ
ゲン化アルキン、例えば、塩化プロパルギル、臭化プロ
パルギル、１−プロモーブテン−２等があげられ、０１
〜ｃ６のポリハロゲン化アルキル、例えば、クロロジフ
ルオロメタン、１−ブロモ−２−クロロプロパン等があ
げられ、０３〜ＣＧのポリハロゲン化アルケン、例えば
、■、３−ジクロロプロペンー１．２，３−ジクロロプ
ロペン−１等があげられ、０２〜Ｃ６のハロゲン化アル
キルチオ−アルカン、例えば、クロロエチルチオメタン
、１−ブロモ−２−メチルチオエタン等があげられる。More specifically, it is desirable that the raw material carbonates be as dry as possible and contain no moisture. The non-aqueous solvent used is preferably an aprotic polar solvent in order to increase the reaction rate, such as acetone, methyl ethyl ketone, acetonitrile, propionitrile, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, etc. alone or in combination. It can be used. As the alkali carbonate salt, for example, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, etc. are used, but sodium carbonate or potassium carbonate is suitable.
It is desirable to use 2 to 3 moles or more of any of these anhydrides based on the nitrocarbonate. Examples of the alkylating agent include halogenated alkyls of 01 to CG, such as methyl iodide, ethyl bromide, isopropyl bromide, isobutyl bromide, hexyl chloride, cyclohexyl chloride, etc., and halogenated alkenes of 03 to CG, such as ,
Allyl chloride, 1-chloro-butene-2,1-chloro-3
-Methyl-butene-2, etc., 03-C6 halogenated alkynes, such as propargyl chloride, propargyl bromide, 1-promobutene-2, etc., 01
-C6 polyhalogenated alkyls, such as chlorodifluoromethane, 1-bromo-2-chloropropane, etc.; 03-CG polyhalogenated alkenes, such as ■,3-dichloropropene-1.2,3- Examples include dichloropropene-1, and 02 to C6 halogenated alkylthio-alkanes, such as chloroethylthiomethane and 1-bromo-2-methylthioethane.
反応は、常圧ないし加圧下で行い、通常３０℃乃至１５
０℃で進行するか、５０℃乃至１２０’ｃが望ましい。The reaction is carried out under normal pressure or increased pressure, usually at a temperature of 30°C to 15°C.
It is preferable to proceed at 0°C or 50°C to 120'C.
一般式（１）で示したカーボネートは、一般式（３）（
式中Ｒは、前記の通り）で表されるフェノールをアルカ
リ水溶液に溶解し、ホスゲンを導入することにより得ら
れる一般式（４）（式中Ｒは、前記の通り）で示される
カーボネートを、硝酸でニトロ化することにより得られ
る。The carbonate represented by general formula (1) is represented by general formula (3) (
A carbonate represented by the general formula (4) (wherein R is as described above) obtained by dissolving a phenol represented by the formula (R is as described above) in an alkaline aqueous solution and introducing phosgene, Obtained by nitration with nitric acid.
以下に、実施例を示し、より具体的に説明する。Examples will be shown below to explain more specifically.
実施例−１
乾燥したビス（２−クロロ−４−フルオロ−５−ニトロ
フェニル）カーボネート６．１４ｇと、炭酸カリウム２
．４８ ｇ、アセトニトリル３０ｍ１を１時間撹拌還流
し、次いで、プロパルギルブロマイド３．９３ｇを加え
２時間撹拌還流を行った。反応終了後不溶物を手刈し、
溶媒を減圧留去し、残渣を塩化メチレン５０ｍ１にとか
し、５％苛性ソーダ水で、次いで水で洗浄し、溶媒を留
去すると、６．７ｇの４−クロロ−２−フルオロ−５−
プロパルギルオキシ−ニトロベンゼンを得た。収率９７
％。このものは、ガスクロ分析によると、純度９９．６
％を示した。このもの−一部をヘキサン−ベンゼン混合
溶媒で再結晶すると、融点８９．５’〜９０，５℃を示
した。Example-1 6.14 g of dry bis(2-chloro-4-fluoro-5-nitrophenyl) carbonate and 2 g of potassium carbonate
．． 48 g of acetonitrile and 30 ml of acetonitrile were stirred and refluxed for 1 hour, and then 3.93 g of propargyl bromide was added and stirred and refluxed for 2 hours. After the reaction is complete, remove the insoluble matter by hand,
The solvent was distilled off under reduced pressure, the residue was dissolved in 50 ml of methylene chloride, washed with 5% aqueous sodium hydroxide and then with water, and the solvent was distilled off to give 6.7 g of 4-chloro-2-fluoro-5-
Propargyloxy-nitrobenzene was obtained. Yield 97
%. According to gas chromatography, this product has a purity of 99.6
%showed that. When a part of this product was recrystallized from a hexane-benzene mixed solvent, it showed a melting point of 89.5' to 90.5°C.
比較例−１
一方、２−’１０ロー４−フルオロー５−ニトロフェノ
ールと炭酸カリウムとをアセトニトリル中で加熱し、次
いでプロパルギルブロマイドと反応させ、同様に処理し
た場合の、４−クロロ−２＝フルオロ−５−プロパルギ
ルオキシニトロベンゼンの収率は９０％であり、純度は
９８．５％であった。Comparative Example 1 On the other hand, when 2-'10-4-fluoro-5-nitrophenol and potassium carbonate were heated in acetonitrile and then reacted with propargyl bromide and treated in the same manner, 4-chloro-2-fluoro The yield of -5-propargyloxynitrobenzene was 90% and the purity was 98.5%.
実施例−２
乾燥したビス（２−クロロ−４−フルオロ−５−ニトロ
フェニル）カーボネート４．８８ｇ−と、炭酸カリウム
１．７３．とを４０ｍ１のアセトニトリル中で３０分間
撹拌還流し、次いでイソプロピルブロマイド３．０８ｇ
を加え、オートクレーブ中で１１０℃２時間反応させた
。反応終了後、不溶物をン戸数し、溶媒を減圧で留去し
、残渣を塩化メチレン５０ｍ１に溶解し、５％苛性ソー
ダ水で、次いで水で洗浄し、溶媒を留去すると、５．０
ｇの４−クロロ−２−フルオロ−５−インプロポキシ−
ニトロベンゼンを淡黄色の結晶として得た。このもの＼
純度はガスクロ分析によると９９．９％であった。一部
をｎ−ヘキサンで再結晶すると、融点６１°〜６２℃を
示した。Example 2 4.88 g of dry bis(2-chloro-4-fluoro-5-nitrophenyl) carbonate and 1.73 g of potassium carbonate. were stirred and refluxed in 40 ml of acetonitrile for 30 minutes, and then 3.08 g of isopropyl bromide was added.
was added and reacted in an autoclave at 110°C for 2 hours. After the reaction, insoluble matter was removed, the solvent was distilled off under reduced pressure, the residue was dissolved in 50 ml of methylene chloride, washed with 5% caustic soda water and then with water, and the solvent was distilled off.
g of 4-chloro-2-fluoro-5-inpropoxy-
Nitrobenzene was obtained as pale yellow crystals. This thing\
Purity was 99.9% according to gas chromatography. When a portion was recrystallized from n-hexane, it showed a melting point of 61° to 62°C.
比較例−２
一方、２−クロロ−４−フルオロ−５−二トロフェノー
ルをイソプロパツールにとかし、２０％苛性ソーダ水溶
液を、原料の該フェノールに対し、１．２倍量加え、イ
ソプロピルブロマイドと１１０℃で２時間反応させ、同
様の方法で単離した所、得られた生成物は黒褐色の油状
物であり、ガスクロ分析の結果、目的物である４−クロ
ロ−２−フルオロ−５−インプロポキシニトロベンゼン
は７５％しか含まれておらず、２０％の４−クロロ−２
，５−ジイソプロポキシニトロベンゼンを含む混合物で
あった。Comparative Example-2 On the other hand, 2-chloro-4-fluoro-5-nitrophenol was dissolved in isopropanol, 20% caustic soda aqueous solution was added in an amount of 1.2 times the amount of the phenol as a raw material, and 110 The product was reacted at ℃ for 2 hours and isolated in the same manner, and the obtained product was a dark brown oil. As a result of gas chromatography, the target product, 4-chloro-2-fluoro-5-impropoxy. Nitrobenzene contains only 75% and 20% 4-chloro-2
, 5-diisopropoxynitrobenzene.
Claims (1)
ずれかを表す）で示されるフェニルカーボネートと、 ▲数式、化学式、表等があります▼（１） Ｒ′Ｘ（Ｒ′は、Ｃ＿１〜Ｃ＿６のアルキル基、シクロ
アルキル基、Ｃ＿３〜Ｃ＿６のアルケニル基、Ｃ＿３〜
Ｃ＿６のアルキニル基、Ｃ＿１〜Ｃ＿６のハロゲン化ア
ルキル基、Ｃ＿３〜Ｃ＿６のハロゲン化アルケニル基、
Ｃ＿２〜Ｃ＿６のアルキルチオアルキル基のいずれかを
表し、Ｘはハロゲン原子を表す）とを非水溶媒中、炭酸
アルカリ塩の存在下で反応させることを特徴とする、一
般式（２）（式中Ｒ、Ｒ′は、前記の通り） ▲数式、化学式、表等があります▼（２） で示されるフッ素化ニトロベンゼン類の製造方法。[Claims] A phenyl carbonate represented by the general formula (1) (in which R represents either a hydrogen atom or a halogen atom), and ▲There are numerical formulas, chemical formulas, tables, etc.▼(1) R' X (R' is a C_1 to C_6 alkyl group, a cycloalkyl group, a C_3 to C_6 alkenyl group, C_3 to
C_6 alkynyl group, C_1 to C_6 halogenated alkyl group, C_3 to C_6 halogenated alkenyl group,
represents any of C_2 to C_6 alkylthioalkyl groups, and X represents a halogen atom) in a non-aqueous solvent in the presence of an alkali carbonate salt. R and R' are as described above) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) Method for producing fluorinated nitrobenzenes shown in (2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62321047A JPH01163157A (en) | 1987-12-18 | 1987-12-18 | Production of fluorinated nitrobenzenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62321047A JPH01163157A (en) | 1987-12-18 | 1987-12-18 | Production of fluorinated nitrobenzenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01163157A true JPH01163157A (en) | 1989-06-27 |
Family
ID=18128209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62321047A Pending JPH01163157A (en) | 1987-12-18 | 1987-12-18 | Production of fluorinated nitrobenzenes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01163157A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496347A2 (en) * | 1991-01-22 | 1992-07-29 | Sagami Chemical Research Center | Methods of preparing fluorobenzene derivatives and related compounds |
-
1987
- 1987-12-18 JP JP62321047A patent/JPH01163157A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496347A2 (en) * | 1991-01-22 | 1992-07-29 | Sagami Chemical Research Center | Methods of preparing fluorobenzene derivatives and related compounds |
| US5281742A (en) * | 1991-01-22 | 1994-01-25 | Sagami Chemical Research Center | Bis(fluorophenyl) carbonate derivatives |
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