JPS61207351A - Chlorination of phenol - Google Patents
Chlorination of phenolInfo
- Publication number
- JPS61207351A JPS61207351A JP60047455A JP4745585A JPS61207351A JP S61207351 A JPS61207351 A JP S61207351A JP 60047455 A JP60047455 A JP 60047455A JP 4745585 A JP4745585 A JP 4745585A JP S61207351 A JPS61207351 A JP S61207351A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- sulfides
- phosphine
- phenyl
- 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.)
- Granted
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000005660 chlorination reaction Methods 0.000 title abstract description 7
- 150000002825 nitriles Chemical class 0.000 claims abstract description 5
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003003 phosphines Chemical class 0.000 claims abstract description 5
- WSANLGASBHUYGD-UHFFFAOYSA-N sulfidophosphanium Chemical class S=[PH3] WSANLGASBHUYGD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000004714 phosphonium salts Chemical class 0.000 claims abstract description 4
- 150000003457 sulfones Chemical class 0.000 claims abstract description 4
- 150000003462 sulfoxides Chemical class 0.000 claims abstract description 4
- 125000003748 selenium group Chemical class *[Se]* 0.000 claims abstract description 3
- 150000004763 sulfides Chemical class 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 150000002019 disulfides Chemical class 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000012320 chlorinating reagent Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 7
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229940090668 parachlorophenol Drugs 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 235000013832 Valeriana officinalis Nutrition 0.000 description 1
- 244000126014 Valeriana officinalis Species 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 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
- WJCXADMLESSGRI-UHFFFAOYSA-N phenyl selenohypochlorite Chemical compound Cl[Se]C1=CC=CC=C1 WJCXADMLESSGRI-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 235000016788 valerian Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、パラクロロフェノールに豊むクロロフェノ
ールが得られるフェノールの塩素化法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) This invention relates to a process for chlorinating phenol that yields chlorophenol enriched in parachlorophenol.
（従来技術）
パラクロロフェノールは工業的、医薬的或いは農薬の中
間体として重要な１し金物である。通常パラクロロフェ
ノールは塩素又はスルフリルクロライド等の塩素１１Ｓ
剤によりフェノールを塩素化させることによシ得られる
。(Prior Art) Parachlorophenol is an important metal as an intermediate for industrial, pharmaceutical, or agricultural chemicals. Usually parachlorophenol is chlorine or chlorine 11S such as sulfuryl chloride.
It is obtained by chlorinating phenol with a chemical agent.
（発明が解決しようとする問題点）
しかし、上述の塩素化法において、スル７リルクロライ
ドを使用した場合はパラクロロフェノールに富む塩素化
が可能であるが、亜硫酸ガスの発生を伴い、公害上の大
きな問題を含み、設備的にも多くの難点があり、塩素に
よる塩素１ｔ、反応ではオルソクロロフェノールに畳ム
クロロフェノールカ得うレ、クロロフェノール中のパラ
とオルソの比（Ｐ１０比）は１．６５程度にしかならな
い。(Problem to be solved by the invention) However, in the above-mentioned chlorination method, when sul7lyl chloride is used, it is possible to achieve chlorination rich in parachlorophenol, but it is accompanied by the generation of sulfur dioxide gas, which causes pollution problems. Including the big problem of chlorophenol, there are many difficulties in terms of equipment.One ton of chlorine is used in the reaction. It becomes only about 1.65.
この発明は上記実情に鑑みフェノールのＰ位に選択性の
あるフェノールの塩素１し法を提案することを目的とす
る。In view of the above circumstances, it is an object of the present invention to propose a method for removing chlorine from phenol, which is selective to the P-position of phenol.
（問題点を解決するための手段）
以上の問題を解決するため、この発明では、フェノール
をホスフィン類、フォスフインオキサイド類、ホスフィ
ンサルファイド類、ホスホニウム塩、スルフィド類、ジ
スルフィド類、スルホキシド類、スルホン類、セレニウ
ム塩、ニトリル類の１種又は２ｆｉｉ以上の存在下で塩
素を塩素１１Ｓ剤として反応させる方法を提案するもの
である。(Means for Solving the Problems) In order to solve the above problems, in the present invention, phenol can be converted into phosphines, phosphine oxides, phosphine sulfides, phosphonium salts, sulfides, disulfides, sulfoxides, and sulfones. The present invention proposes a method in which chlorine is reacted as a chlorine 11S agent in the presence of one or more of nitrites, selenium salts, and nitriles.
ここでホスフィン類、フォスフインオキサイド類は、Ｒ
，Ｐ 、 Ｒ，ＰＯで表わされ、例えば、Ｒ炭素数１か
ら８１でのアルキル基の１種又は２種以上から選ばれた
化合物を使用することができる。Here, phosphines and phosphine oxides are R
, P , R, PO, for example, a compound selected from one or more alkyl groups in which R has 1 to 81 carbon atoms can be used.
ホスフィンサルファイド類、ホスホニウム塩は、Ｒ，Ｐ
Ｓ、 Ｒ，ＰＸで表わされ、例えば、Ｒがフェニル基、
ベンジル基、炭素数１から８までのアルキル基、メトキ
シメチル基の１１１ｉ又は２′！ｊ１以上から選ばれ、
且つ、Ｘはｃｔ又はＢｒから選ばれた化合物を使用する
ことができる。Phosphine sulfides and phosphonium salts are R, P
Represented by S, R, PX, for example, R is a phenyl group,
111i or 2' of a benzyl group, an alkyl group having 1 to 8 carbon atoms, and a methoxymethyl group! Selected from j1 or above,
Moreover, a compound selected from ct or Br can be used as X.
スルフィド類はＲ２Ｓで表わされ、例えば、Ｒがフェニ
ル基、ベンジル基、フェニルエチル基、炭素数１〜４ま
でのアルキル基の１種又は２種以上から選ばれた化合物
を使用することができる。更にジスルフィド類としては
、テトラメチルチウラムジスルフィドを使用することが
できる。Sulfides are represented by R2S, and for example, compounds in which R is selected from one or more of phenyl group, benzyl group, phenylethyl group, and alkyl group having 1 to 4 carbon atoms can be used. . Further, as the disulfide, tetramethylthiuram disulfide can be used.
また、スルホキシド類はＲ，Ｓｏで表わされ、例えば、
Ｒが炭素数１から４までのアルキル基、フェニル基、ベ
ンジル基、クレジルＭ、ｔ−７”チルフェニル基の１ｍ
又は２種以上から選ばれた１１Ｉ、金物を使用すること
ができる。In addition, sulfoxides are represented by R, So, for example,
1m where R is an alkyl group having 1 to 4 carbon atoms, phenyl group, benzyl group, cresyl M, t-7" tylphenyl group
Alternatively, 11I and hardware selected from two or more types can be used.
スルホン類は、Ｒ，８０，で表わされ、例えば、Ｒがメ
トキシ基、エトキシ基、フェノキシ基、クレジル基の１
種又は２種以上から選ばれた化合物を使用することがで
きる。Sulfones are represented by R,80, for example, R is a methoxy group, an ethoxy group, a phenoxy group, or a cresyl group.
Compounds selected from one species or two or more species can be used.
セリウム塩は、Ｒ８ｅＸで表わされ、例えば、Ｒがフェ
ニル基、メチルフェニル基、ベンジル基、且つＸＦｉＣ
ｌ又はＢＴから選ばれた化合物を使用することができる
。The cerium salt is represented by R8eX, for example, R is a phenyl group, methylphenyl group, benzyl group, and XFiC
Compounds selected from 1 or BT can be used.
ニトリル類はＲＣＮで表わされ、例えば、Ｒ−ＡＸ炭素
数１〜４のアルキル基から選ばれた化合物を使用するこ
とができる。Nitriles are represented by RCN, and for example, a compound selected from R-AX, an alkyl group having 1 to 4 carbon atoms, can be used.
なお、これ等の触媒は単独で使用することができるが、
２種以上を混合して、使用してもよく、またこれらの触
媒にＭＸｎ（Ｍは’Ｉ’４．Ｆ、、Ｎ４、Ｃｏ、 Ｃｓ
、 Ａｌ ％Ｓ％Ｓｎ％８ｇ％Ｓｂ％ＸはＣｌ又はＱ
ｎ２１〜３）で表わされるルイス酸を助触媒として加
えてもよ−。Note that these catalysts can be used alone, but
Two or more types may be mixed and used, and these catalysts may include MXn (M is 'I'4.F, N4, Co, Cs
, Al%S%Sn%8g%Sb%X is Cl or Q
A Lewis acid represented by n21-3) may be added as a promoter.
上記触媒の添加量は、フェノールに対して、１〜５０ｗ
ｔ４好ましくは５〜１０ｗｔＬｌｂであり、１ ｗｔ％
以下では触媒効果が弱（，５０ｗｔ％以上では効果があ
っても経済的には得策とはいい難い。また、反応温度は
４５〜１５０℃、好ましくは７０〜８０℃で塩素１Ｌ剤
として塩素ガスを導入してフェノールの塩素化反応を行
う。こ＼で反応温度を４５〜１５０℃としたのは、４５
℃以下ではフェノールの凝固点の４０℃以上で反応させ
る為であり、１５０℃以上では排ガス中にフェノール類
の飛沫同伴による飛散が多くなる常置が起きやすい。The amount of the above catalyst added is 1 to 50w relative to phenol.
t4 is preferably 5 to 10 wtLlb, and 1 wt%
Below 50 wt%, the catalytic effect is weak (and above 50 wt%, even if it is effective, it is not economical. Also, the reaction temperature is 45 to 150 °C, preferably 70 to 80 °C, and chlorine gas as a chlorine 1L agent is The chlorination reaction of phenol is carried out by introducing
If the temperature is below 150°C, the reaction will occur at 40°C or higher, which is the freezing point of phenol, and if the temperature is above 150°C, there will be a tendency for the phenol to be left in the exhaust gas with a large amount of entrained droplets.
また、塩素１１Ｚ反応は常圧、加圧、減圧のいずれの状
態で行わせてもよいが、通常は排ガスを適切に排出させ
る為に、常圧〜水柱０．５〜２ｍ程度の減圧で反応を行
なわせる。In addition, the chlorine 11Z reaction may be carried out under normal pressure, increased pressure, or reduced pressure; however, in order to properly discharge exhaust gas, the reaction is usually carried out at normal pressure to reduced pressure of about 0.5 to 2 m of water column. have them do it.
（発明の効果）
以上の塩素化反応により ｐ／Ｑ比を平均２．０機度に
高めることができる。(Effect of the invention) The above chlorination reaction can increase the p/Q ratio to an average of 2.0 degrees.
また、この発明に使用する触媒は繰返して使用しても、
活性の低下なく、耐久性に関して優れた性質を有し、し
たがって、この発明はパラクロロフェノールの製法とし
て、その工業的価値は極めて高い。Moreover, even if the catalyst used in this invention is used repeatedly,
It has excellent properties in terms of durability without a decrease in activity, and therefore, the present invention has extremely high industrial value as a method for producing parachlorophenol.
（実施例） 以下この発明の実施例を示す。(Example) Examples of this invention will be shown below.
実施例（１）
かきまぜ機、温度計、塩素ガス導入管、ガス排水管、冷
却器を備えた５〇−反応フラスコにフェノール２０ｇｔ
、、および、上記触媒の内トリフェニルホスフィンｐｈ
！、Ｐ２ｇ乞を仕込み、ｆｆｌ押下、８０℃で塩素ガス
を導入し反応させた。反応は、ガスクロマトグラフィー
により追跡し、ジクロル体の増加が始まる時期で、未反
応フェノールが約１０チ程度の領域をもって、反応の終
了とし、Ｐｌｏで表示した時２．５５であった。更に繰
返しの触媒効果を検する為に反応物を脱酸後、減圧蒸溜
で、塩化フェノールを溜去し、釜残として残溜した触媒
に新たにフェノールを２０ｑｒ、加えて前記同様に塩素
を導入し反応を繰返した結果繰返し回数 ２５４５６
７８
Ｐｌｏ 値 ２．３５ ２．０６ ２．１９ ２
．０６ ２．０７ ２．０２ ２．２Ｂ等となり、安定
した効果で触媒の繰返し使用が可能であった。Example (1) 20 g of phenol was placed in a 50-kg reaction flask equipped with a stirrer, a thermometer, a chlorine gas inlet pipe, a gas drain pipe, and a condenser.
, , and among the above catalysts, triphenylphosphine ph
! , P2g was charged, ffl was pressed, and chlorine gas was introduced at 80°C to cause a reaction. The reaction was monitored by gas chromatography, and the reaction was considered to have ended when the amount of unreacted phenol started to increase and the amount of unreacted phenol was approximately 10 cm, and the value was 2.55 when expressed as Plo. Furthermore, in order to repeatedly test the catalytic effect, after deoxidizing the reactant, the chlorinated phenol was distilled off under reduced pressure, and 20 qr of new phenol was added to the catalyst remaining as a residue in the pot, and chlorine was introduced in the same manner as above. As a result of repeating the reaction, the number of repetitions is 25456
78 Plo value 2.35 2.06 2.19 2
．． 06 2.07 2.02 2.2B, etc., and the catalyst could be used repeatedly with stable effects.
実施例（２）
実施例（１）と同様の反応装置にフェノール２１Ｈ１ｒ
と触媒として、ベンジルトリフェニルホスホニウムクロ
ライドＱＣＨ，Ｐ（○）ｓｃｌ １１７ｒ、 を仕込
み、前同様に反応した時、Ｐ力値は２．０９であった。Example (2) Phenol 21H1r was added to the same reactor as Example (1).
and benzyltriphenylphosphonium chloride QCH, P(○)scl 117r, as a catalyst and reacted in the same manner as before, the P force value was 2.09.
又実施例（１）と同様にして触媒の繰返し効力を測定し
た結果
繰返し回数 ２ ５ ４ ５ ６ ７ ８ ９ １０Ｐ
１０値２，０７２Ｊ］７２Ｊ］２２．０２２０１冗０１
．９４１．９９１．９７等となり、安定した効力で触媒
の繰返し使用が可能であった。In addition, the repeated effectiveness of the catalyst was measured in the same manner as in Example (1), and the results showed that the number of repetitions was 2 5 4 5 6 7 8 9 10P
10 value 2,072J] 72J] 22.02201 redundancy 01
．． 941.991.97, etc., and the catalyst could be used repeatedly with stable efficacy.
実施例（３） 実施例（１）と同様の反応装置にフェノール２０９ｒ。Example (3) Phenol 209r was placed in the same reactor as in Example (1).
と触媒としてフェニルセレニルクロライドＰ１０は、
繰返し回数 ２ ５ ４ ５ ６ ７ ８ ９ １０Ｐ
１０ （ＦＬ ２．！９２．１０２．１１ ＺＯＯ凹５
１．９８１．９５１Ｊ３８１Ｊ３１等となシ、安定した
効力で触媒の繰返し使用が可能であった。and phenylselenyl chloride P10 as a catalyst.Number of repetitions 2 5 4 5 6 7 8 9 10P
10 (FL 2.!92.102.11 ZOO concave 5
1.981.951J381J31 etc., the catalyst could be used repeatedly with stable efficacy.
なお、他の実施例については、その条件と実施結果だけ
を以下に示す。In addition, regarding other examples, only the conditions and implementation results are shown below.
壓”−’６ ｋ Ｃｆ） ＞ −−ｐ ＝ 、 −〇
−６哨 寸 ク
ロロ膿ロクロぐ口ぐ口０口へ
ｃａｒ ｅ” ａｓ 、Ｌ ａｓ −：
ａｓ 、： ａｓ ｃａｒ ＝ ＝ ｅｓ
クロロＯロ ロ クロロ
へＮ へ へ へ へへへ
＋ｏｒ＋＋ Φ か ロ
− 国 哨−−−Ｐ Ｎ
〜 へ 〜２４２０ 硫１しエチル
ｚ５２０ ジメチルスルホキシド
２６ ２Ｇ 硫化フェニル
２７ ２０ 硫１ζｎ−ブチル
２８２０ 硫１１１Ｓメチル
２９２０ 硫化ベンジル
３０２０ ジフェニルスルホン
５１ ２０ α−７エールエチルスルフイド５２
２０ テトラメチルチウラムジスルフィドｓｓ
ｚｏ ｎ−ブチロニトリル５４ ２０ Ｋ
−吉草識二トリル５５ ２０ ベンジルトリ７
二二ルホニウムクロライド三塩１こアンチモン壓”−'6 k Cf) > −−p = , −〇
-6 minutes Car e” as, Las -:
as,: as car = = es
Chloro O Lo Lo Chloro to N To To To He To +or++ Φ Or To
- National Guard---P N
~ to ~2420 sulfur 1 ethyl z520 dimethyl sulfoxide 26 2G phenyl sulfide 27 20 sulfur 1ζn-butyl 2820 sulfur 111S methyl 2920 benzyl sulfide 3020 diphenyl sulfone 51 20 α-7 ale ethyl sulfide 52
20 Tetramethylthiuram disulfide ss
zo n-butyronitrile 54 20K
- Valerian Nitrile 55 20 Benzyltrile 7
1 antimony 22 sulfonium chloride trisalt
Claims (2)
イド類、ホスフィンサルファイド類、ホスホニウム塩、
スルフィド類、ジスルフィド類、スルホキシド類、スル
ホン類、セレニウム塩、ニトリル類の１種又は２種以上
の存在で塩素化剤と反応させることを特徴とするフェノ
ールの塩素化法。(1) Phenol can be used as phosphines, phosphine oxides, phosphine sulfides, phosphonium salts,
A method for chlorinating phenol, which comprises reacting with a chlorinating agent in the presence of one or more of sulfides, disulfides, sulfoxides, sulfones, selenium salts, and nitriles.
第１項記載のフェノールの塩素化法。(2) A method for chlorinating phenol according to claim 1, which uses a Lewis acid as a promoter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60047455A JPS61207351A (en) | 1985-03-12 | 1985-03-12 | Chlorination of phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60047455A JPS61207351A (en) | 1985-03-12 | 1985-03-12 | Chlorination of phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61207351A true JPS61207351A (en) | 1986-09-13 |
| JPS6256140B2 JPS6256140B2 (en) | 1987-11-24 |
Family
ID=12775619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60047455A Granted JPS61207351A (en) | 1985-03-12 | 1985-03-12 | Chlorination of phenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61207351A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6391342A (en) * | 1986-09-25 | 1988-04-22 | ローヌ‐プーラン・シミ | Stabilization of mixture obtained by chlorination of phenol and/or chlorophenol |
| JPS6393744A (en) * | 1986-09-25 | 1988-04-25 | ローヌープーラン・シミ | Manufacture of chlorophenols |
| JPS63115837A (en) * | 1986-09-25 | 1988-05-20 | ローヌ‐プーラン・シミ | Stabilization of chlorination mixture of phenol and/or chlorophenol |
| FR2618144A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | PROCESS FOR CHLORINATION OF PHENOLIC COMPOUNDS |
| FR2618146A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF 2,4,6-TRICHLORO-PHENOL |
| FR2618145A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | METHOD FOR SELECTIVE CHLORINATION OF PHENOLIC COMPOUNDS |
| CN109096057A (en) * | 2018-10-15 | 2018-12-28 | 连云港恒贸化工有限公司 | A kind of technical process of tower continuous chlorination production parachlorophenol |
-
1985
- 1985-03-12 JP JP60047455A patent/JPS61207351A/en active Granted
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6391342A (en) * | 1986-09-25 | 1988-04-22 | ローヌ‐プーラン・シミ | Stabilization of mixture obtained by chlorination of phenol and/or chlorophenol |
| JPS6393744A (en) * | 1986-09-25 | 1988-04-25 | ローヌープーラン・シミ | Manufacture of chlorophenols |
| JPS63115837A (en) * | 1986-09-25 | 1988-05-20 | ローヌ‐プーラン・シミ | Stabilization of chlorination mixture of phenol and/or chlorophenol |
| FR2618144A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | PROCESS FOR CHLORINATION OF PHENOLIC COMPOUNDS |
| FR2618146A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF 2,4,6-TRICHLORO-PHENOL |
| FR2618145A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | METHOD FOR SELECTIVE CHLORINATION OF PHENOLIC COMPOUNDS |
| US5149858A (en) * | 1987-07-17 | 1992-09-22 | Rhone-Poulenc Chimie | Selective ortho-chlorination of phenols |
| CN109096057A (en) * | 2018-10-15 | 2018-12-28 | 连云港恒贸化工有限公司 | A kind of technical process of tower continuous chlorination production parachlorophenol |
| CN109096057B (en) * | 2018-10-15 | 2020-10-23 | 连云港恒贸化工有限公司 | Process for producing p-chlorophenol by tower-type continuous chlorination method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6256140B2 (en) | 1987-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0729932A1 (en) | Method of producing halopropane | |
| JPS61207351A (en) | Chlorination of phenol | |
| EP0126669B1 (en) | N-substituted phenothiazine derivative as a catalyst for the nuclear chlorination of aromatic hydrocarbons | |
| KR20040104406A (en) | Process for the synthesis of aryl sulfurpentafluorides | |
| US6927305B2 (en) | Process for production of alkanesulfonic acid | |
| TWI295986B (en) | ||
| JPS6026772B2 (en) | Alkylbenzene chlorination method | |
| CA1067521A (en) | Process for the production of chlorofluorinated aromatic hydrocarbons | |
| FR2617836A1 (en) | SYNTHESIS OF PERFLUOROALKYL BROMIDES | |
| JP5021745B2 (en) | Method for producing fluoromethyl 2,2,2-trifluoro-1- (trifluoromethyl) ethyl ether | |
| US20050272959A1 (en) | Method of producing cumene hydroperoxide | |
| JPS59155341A (en) | Manufacture of fluorinated nitroalkane | |
| CA1084531A (en) | Processes for the preparation of chlorinated phenols | |
| JP7208976B2 (en) | Method for producing fluorine-containing sulfide compound | |
| JP3557624B2 (en) | Method for producing 4,6-dinitrohalobenzene | |
| TW200421977A (en) | Novel process for the preparation of a synthetic intermediate for pesticides | |
| EP0150587B1 (en) | Preparation of chlorobenzotrifluoride compounds | |
| US5072062A (en) | Bromination method | |
| EP0113513B1 (en) | Production of 1,2-dichloroethane | |
| JPH08239333A (en) | Production of 1,1,1,3,3-pentachloropropane | |
| US4716254A (en) | Preparation of aromatic iodine compounds | |
| CN1074308C (en) | Fluid and catalyst for the preparation of aromatic nitrile halide | |
| TWI341828B (en) | Method of removing water from hydrofluorocarbon manufacturing processes | |
| CN1286244A (en) | Method for preparing 2-chloro-4-nitroalkylbenzene | |
| JPS61109745A (en) | Manufacture of 2,4,5-trichlorophenol |