JPH03127753A - Production of 4-chloro-4'-hydroxybenzophenones - Google Patents
Production of 4-chloro-4'-hydroxybenzophenonesInfo
- Publication number
- JPH03127753A JPH03127753A JP1263411A JP26341189A JPH03127753A JP H03127753 A JPH03127753 A JP H03127753A JP 1263411 A JP1263411 A JP 1263411A JP 26341189 A JP26341189 A JP 26341189A JP H03127753 A JPH03127753 A JP H03127753A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- chloro
- fluoroalkanesulfonic
- chlorobenzoic
- reaction
- 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 6
- RUETVLNXAGWCDS-UHFFFAOYSA-N (4-chlorophenyl)-(4-hydroxyphenyl)methanone Chemical class C1=CC(O)=CC=C1C(=O)C1=CC=C(Cl)C=C1 RUETVLNXAGWCDS-UHFFFAOYSA-N 0.000 title description 11
- 239000002253 acid Substances 0.000 claims abstract description 28
- -1 para-chlorobenzoyl halides Chemical class 0.000 claims abstract description 13
- XXXJKBSLNRMHLH-UHFFFAOYSA-N phenyl 4-chlorobenzoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OC1=CC=CC=C1 XXXJKBSLNRMHLH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000007513 acids Chemical class 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000000242 4-chlorobenzoyl group Chemical group ClC1=CC=C(C(=O)*)C=C1 0.000 claims description 5
- NMXYTAOBIVNSDM-UHFFFAOYSA-N (4-chloro-4-hydroxycyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical class C1=CC(O)(Cl)CC=C1C(=O)C1=CC=CC=C1 NMXYTAOBIVNSDM-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005618 Fries rearrangement reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 150000002989 phenols Chemical class 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 3
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PYTMYNQWASSKJH-UHFFFAOYSA-N (4-chlorophenyl)-(2-hydroxyphenyl)methanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=C(Cl)C=C1 PYTMYNQWASSKJH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- JYFJHKRWGLEWKH-UHFFFAOYSA-N (4-chloro-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 JYFJHKRWGLEWKH-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical class C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 1
- ONVNRYJOMHDJER-UHFFFAOYSA-N 4-chloro-2,6-dimethylbenzoic acid Chemical compound CC1=CC(Cl)=CC(C)=C1C(O)=O ONVNRYJOMHDJER-UHFFFAOYSA-N 0.000 description 1
- AOGAFBUEYBRUNY-UHFFFAOYSA-N 4-chloro-2,6-dimethylbenzoyl chloride Chemical compound CC1=CC(Cl)=CC(C)=C1C(Cl)=O AOGAFBUEYBRUNY-UHFFFAOYSA-N 0.000 description 1
- XXFKOBGFMUIWDH-UHFFFAOYSA-N 4-chloro-2-methylbenzoic acid Chemical compound CC1=CC(Cl)=CC=C1C(O)=O XXFKOBGFMUIWDH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- CGDXUTMWWHKMOE-UHFFFAOYSA-N difluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)F CGDXUTMWWHKMOE-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、農薬、医薬、耐熱性ポリマーなどの原料また
は中間体として有用な化合物である４−クロロ−４′−
ヒドロキシベンゾフェノン類の製造法に関するものであ
る。Detailed Description of the Invention [Industrial Application Field] The present invention relates to 4-chloro-4'- which is a compound useful as a raw material or intermediate for agricultural chemicals, medicines, heat-resistant polymers, etc.
This invention relates to a method for producing hydroxybenzophenones.
［従来の技術１
１−
４−クロロ−４゛−ヒドロキシベンゾフェノン類の製造
法としては、塩化パラクロロベンゾイルとフェノールを
塩化アルミニウムなどのルイス酸の存在下、フリーデル
・クラフッ反応を行う方法が一般的に知られている。ま
た、塩化パラクロロベンゾイルとフェノールからエステ
ルを合威し、塩化アルミニウムなどのルイス酸の存在下
、芳香族エステルのフリース部位による方法も知られて
いる。[Prior art 1] A common method for producing 1-4-chloro-4'-hydroxybenzophenones is to perform a Friedel-Krach reaction between parachlorobenzoyl chloride and phenol in the presence of a Lewis acid such as aluminum chloride. is known for. Also known is a method in which an ester is synthesized from parachlorobenzoyl chloride and phenol, and an aromatic ester is used in a fleece moiety in the presence of a Lewis acid such as aluminum chloride.
また、アルカンスルホン酸またはフルオロアルカンスル
ホン酸存在下、４−クロロ安息香酸とフェノールから製
造する方法も提案されている（特開昭５７−４１４０号
公報及び特開昭５８−６２１３２号公報）。Furthermore, a method for producing it from 4-chlorobenzoic acid and phenol in the presence of alkanesulfonic acid or fluoroalkanesulfonic acid has also been proposed (Japanese Patent Laid-Open Nos. 57-4140 and 58-62132).
［発明が解決しようとする問題点］
しかしながら、塩化アルミニウムなどのルイス酸を用い
る場合は、反応生成物とコンプレックス化合物を形成す
るので、目的の生成物を単離するためには水と反応させ
る必要があり、従って塩化アルミニウムは水酸化アルミ
ニウムとなることから、塩化アルミニウムの回収、再使
用は不可能である。[Problems to be solved by the invention] However, when a Lewis acid such as aluminum chloride is used, it forms a complex compound with the reaction product, so it is necessary to react with water in order to isolate the desired product. Therefore, since aluminum chloride becomes aluminum hydroxide, it is impossible to recover and reuse aluminum chloride.
−２＝
また、アルカンスルホン酸あるいはフルオロアルカンス
ルホン酸存在下、４−クロロ安息香酸とフェノールから
直接４−クロロ−４′−ヒドロキシベンゾフェノンを製
造する場合は反応により水が生成することから、大過剰
の上記スルホン酸類を必要とする。加えて、上記スルホ
ン酸類から生成水を分離し、これらの酸を再使用できる
ようにするためにはコスト的に問題があることも知られ
ている。特に、フルオロアルカンスルホン酸は高価な試
剤であることから、極力損失を低くしてリサイクルする
ことが必要である。しかし、現時点ではフルオロアルカ
ンスルホン酸と水とを分離する工業的に有効な方法は見
出されていない。-2= Also, when 4-chloro-4'-hydroxybenzophenone is produced directly from 4-chlorobenzoic acid and phenol in the presence of alkanesulfonic acid or fluoroalkanesulfonic acid, water is produced by the reaction, so there is a large excess. of the above-mentioned sulfonic acids. In addition, it is known that there is a cost problem in separating the produced water from the sulfonic acids so that these acids can be reused. In particular, since fluoroalkanesulfonic acid is an expensive reagent, it is necessary to recycle it with as little loss as possible. However, at present, no industrially effective method for separating fluoroalkanesulfonic acid and water has been found.
また、これまでの方法では目的とする４−クロロ−４゛
−ヒドロキシベンゾフェノンの他に４−クロロ−２゛−
ヒドロキシベンゾフェノンがある程度生成することから
、この異性体を分離する必要がある。特に、４−クロロ
−４゛−ヒドロキシベンゾフェノンをポリエーテルケト
ン等の耐熱性ポリマーの原料として使用する場合、４−
クロロ−２゛−ヒドロキシベンゾ−３＝
フェノンが混入すると、その立体障害のため、重合度が
向上しない等の問題が生じる。このようなことから、４
−クロロ−２′−ヒドロキシベンゾフェノンの副生の少
ない方法が望まれ、この４−クロロ−４゛−ヒドロキシ
ベンゾフェノンと４−クロロ−２−ヒドロキシベンゾフ
ェノンの収率比（以下、パラ／オルト比と略す）を高く
することが望まれていた。In addition to the target 4-chloro-4゛-hydroxybenzophenone, 4-chloro-2゛-
Since some hydroxybenzophenone is formed, it is necessary to separate this isomer. In particular, when using 4-chloro-4'-hydroxybenzophenone as a raw material for heat-resistant polymers such as polyetherketone, 4-
When chloro-2'-hydroxybenzo-3=phenone is mixed, problems arise such as the degree of polymerization not being improved due to its steric hindrance. For this reason, 4
A method that produces less by-product of -chloro-2'-hydroxybenzophenone is desired, and the yield ratio (hereinafter abbreviated as para/ortho ratio) of 4-chloro-4'-hydroxybenzophenone and 4-chloro-2-hydroxybenzophenone is desired. ) was desired to be increased.
［問題を解決するための手段］
本発明者らは、生成物と触媒との分離及び触媒の再使用
が容易であり、かつ４−クロロ−４゛−ヒドロキシベン
ゾフェノンを高選択率で製造できる方法について詳細な
検討を行った結果、４−クロロ安息香酸フェニルエステ
ルを別途台威し、単離した後にフルオロアルカンスルホ
ン酸存在下、４０〜１２０°Ｃの温度範囲でフリース転
位反応を行なうことにより選択的に４−クロロ−４゛−
ヒドロキシベンゾフェノンが生成することを見出し、本
発明に到達したものである。[Means for Solving the Problem] The present inventors have developed a method that allows easy separation of the product and catalyst and reuse of the catalyst, and that can produce 4-chloro-4'-hydroxybenzophenone with high selectivity. As a result of a detailed study, we found that 4-chlorobenzoic acid phenyl ester was prepared separately, isolated, and then subjected to Fries rearrangement reaction in the presence of fluoroalkanesulfonic acid at a temperature of 40 to 120°C. 4-chloro-4゛-
The present invention was achieved by discovering that hydroxybenzophenone is produced.
加えて、本発明の方法では、水が生成しないことから、
フルオロアルカンスルホン酸は反応後、４−
若干の減圧下で蒸発留去させることにより、生成物から
容易に分離でき、再使用も可能である。In addition, since water is not produced in the method of the present invention,
After the reaction, the fluoroalkanesulfonic acid can be easily separated from the product by evaporation and distillation under slightly reduced pressure, and can be reused.
即ち、本発明は、パラクロロ安息香酸類あるいはハロゲ
ン化パラクロロベンゾイル類をパラ位に置換基を持たな
いフェノール類でエステル化して４−クロロ安息香酸フ
ェニルエステルを得、単離し、次いで、その４−クロロ
安息香酸フェニルエステルをフルオロアルカンスルホン
酸存在下、４０〜１２０°Ｃの温度範囲で反応させるこ
とを特徴とする４−クロロ−４′−ヒドロキシベンゾフ
ェノン類の製造法を提供するものである。That is, in the present invention, 4-chlorobenzoic acid phenyl ester is obtained by esterifying parachlorobenzoic acids or halogenated parachlorobenzoyls with a phenol having no substituent at the para position, and the 4-chlorobenzoic acid phenyl ester is isolated. The present invention provides a method for producing 4-chloro-4'-hydroxybenzophenones, which is characterized by reacting benzoic acid phenyl ester in the presence of fluoroalkanesulfonic acid at a temperature range of 40 to 120°C.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
本発明に用いられるパラクロロ安息香酸類は次式（Ｉ）
で表される。The parachlorobenzoic acids used in the present invention have the following formula (I)
It is expressed as
上式（Ｉ）において、ｎは１〜４の整数であり、Ｒ１は
同一であるか、もしくは異なっていてもよく、水素原子
または低級アルキル基を示す。該低級アルキル基の炭素
数は好ましくは１〜３である。In the above formula (I), n is an integer of 1 to 4, and R1 may be the same or different and represents a hydrogen atom or a lower alkyl group. The lower alkyl group preferably has 1 to 3 carbon atoms.
−
パラクロロ安息香酸類の具体例としては、パラクロロ安
息香酸、２−メチル−４−クロロ安息香酸、２．６−シ
メチルー４−クロロ安息香酸などが挙げられる。好まし
くはパラクロロ安息香酸が用いられる。- Specific examples of parachlorobenzoic acids include parachlorobenzoic acid, 2-methyl-4-chlorobenzoic acid, 2,6-dimethyl-4-chlorobenzoic acid, and the like. Preferably parachlorobenzoic acid is used.
また、ハロゲン化パラクロロベンゾイル類は次式（ＩＩ
）で表される。In addition, halogenated parachlorobenzoyls are represented by the following formula (II
).
上式（ＩＩ ）において、ｎ及びＲ１は式（Ｉ）におけ
ると同義である。Ｘはハロゲン原子、すなわちフッ素、
塩素、臭素またはヨウ素を表わす。ハロゲン化パラクロ
ロベンゾイルの具体例としては、フッ化パラクロロベン
ゾイル、塩化パラクロロベンゾイル、臭化パラクロロベ
ンゾイル、ヨウ化パラクロロベンゾイル、２−メチル−
４−クロロベンゾイルクロライド、２，６−シメチルー
４−クロロベンゾイルクロライドなどが挙げられる。好
ましくは塩化パラクロロベンゾイルが用いられる。In the above formula (II), n and R1 have the same meanings as in formula (I). X is a halogen atom, i.e. fluorine,
Represents chlorine, bromine or iodine. Specific examples of halogenated parachlorobenzoyl include parachlorobenzoyl fluoride, parachlorobenzoyl chloride, parachlorobenzoyl bromide, parachlorobenzoyl iodide, and 2-methyl-
Examples include 4-chlorobenzoyl chloride and 2,6-dimethyl-4-chlorobenzoyl chloride. Preferably parachlorobenzoyl chloride is used.
本発明に用いられるパラ位に置換基をもたない６一 フェノール類は次式で表される。6-1 which does not have a substituent at the para position used in the present invention Phenols are represented by the following formula.
上式において、ｍは１〜４の整数であり、Ｒ２は同一で
あるか、もしくは異なっていてもよく、水素原子または
低級アルキル基を示す。該低級アルキル基の炭素数は好
ましくは１〜３である。In the above formula, m is an integer of 1 to 4, and R2 may be the same or different and represents a hydrogen atom or a lower alkyl group. The lower alkyl group preferably has 1 to 3 carbon atoms.
パラ位に置換基をもたないフェノール類の具体例として
は、フェノール、０−クレゾール、ｍ−クレゾール、２
，６−シメチルフエノール、２，６−ジニチルフエノー
ルなどが挙げられる。好ましくはフェノール及び２，６
−シメチルフエノールが用いられる。Specific examples of phenols that do not have a substituent at the para position include phenol, 0-cresol, m-cresol, 2
, 6-dimethylphenol, 2,6-dinitylphenol and the like. Preferably phenol and 2,6
-dimethylphenol is used.
パラクロロ安息香酸あるいはハロゲン化パラクロロベン
ゾイルとフェノールの反応による４−クロロ安息香酸フ
ェニルエステルの合成は公知の方法により定量的に進行
する。例えば、パラクロロ安息香酸とフェノールとの反
応では、触媒として硫酸、パラトルエンスルホン酸、Ｂ
Ｆ、、ポリリン酸、イオン交換樹脂、フッ素化スルホン
酸樹脂等の酸７−
を用いることにより定量的に進行し、収率良く、４−ク
ロロ安息香酸フェニルエステルが得られる。また、特に
塩化パラクロロベンゾイルとフェノールとの反応では、
金属マグネシウム、ジメチルアニリン、ピリジンなどの
触媒を用いるか、あるいはアルカリ水溶液中で反応を行
うことにより、定量的に進行し、反応液を濾過するだけ
で４−クロロ安息香酸フェニルエステルを得ることがで
きる。The synthesis of 4-chlorobenzoic acid phenyl ester by the reaction of parachlorobenzoic acid or halogenated parachlorobenzoyl with phenol proceeds quantitatively by a known method. For example, in the reaction of parachlorobenzoic acid and phenol, sulfuric acid, paratoluenesulfonic acid, B
By using an acid such as F, polyphosphoric acid, ion exchange resin, or fluorinated sulfonic acid resin, the process proceeds quantitatively and 4-chlorobenzoic acid phenyl ester can be obtained in good yield. Also, especially in the reaction between parachlorobenzoyl chloride and phenol,
By using a catalyst such as magnesium metal, dimethylaniline, or pyridine, or by carrying out the reaction in an alkaline aqueous solution, the reaction proceeds quantitatively, and 4-chlorobenzoic acid phenyl ester can be obtained simply by filtering the reaction solution. .
本発明においては、このようにして得られた４−クロロ
安息香酸フェニルエステルを単離し次いでフリース転位
反応に供することにより、純度の高い４−クロロ−４−
ヒドロキシベンゾフェノン類を得ることができる。In the present invention, the 4-chlorobenzoic acid phenyl ester thus obtained is isolated and then subjected to the Fries rearrangement reaction to obtain highly pure 4-chloro-4-
Hydroxybenzophenones can be obtained.
本発明に使用するフルオロアルカンスルホン酸としては
、トリフルオロメタンスルホン酸及びジフルオロメタン
スルホン酸が好ましい。As the fluoroalkanesulfonic acid used in the present invention, trifluoromethanesulfonic acid and difluoromethanesulfonic acid are preferred.
４−クロロ安息香酸フェニルエステルとフルオロアルカ
ンスルホン酸の量比は４−クロロ安息香酸フェニルエス
テル１モル当たり、フルオロアルカンスルホン酸が０．
０１モル以上、好ましくは０．０１〜８−
１００００モル、より好ましくは０．０５〜１０００モ
ルの範囲が採用される。The quantitative ratio of 4-chlorobenzoic acid phenyl ester to fluoroalkanesulfonic acid is 0.00% of fluoroalkanesulfonic acid per mole of 4-chlorobenzoic acid phenyl ester.
A range of 0.01 mol or more, preferably 0.01 to 8-10000 mol, more preferably 0.05 to 1000 mol is adopted.
また、フルオロアルカンスルホン酸を溶媒として使用す
ることも好ましい。もちろん、反応に悪影響を及ぼさな
い範囲で適当な溶媒を用いることも可能である。このよ
うな溶媒としては、ペンタン、ヘキサン、ヘプタン、オ
クタン、ノナン、デカン、シクロペンタン、シクロヘキ
サンなどの脂肪族及び脂環族炭化水素類、ベンゼン、ト
ルエン、キシレン、などの芳香族炭化水素類、四塩化炭
素、塩化メチレン、クロロホルム、ジクロルエタン、ク
ロルベンゼン、ジクロルベンゼン、ブロムベンゼンなど
のハロゲン化炭化水素類、ニトロベンゼンなどの芳香族
ニトロ化合物類、酢酸、プロピオン酸、モノクロル酢酸
、フルオロ酢酸、トリフルオロ酢酸などのカルボン酸類
、メタンスルホン酸、トリフルオロメタンスルホン酸な
どのスルホン酸類などが用いられる。It is also preferred to use fluoroalkanesulfonic acid as a solvent. Of course, it is also possible to use an appropriate solvent as long as it does not adversely affect the reaction. Such solvents include aliphatic and alicyclic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated hydrocarbons such as carbon chloride, methylene chloride, chloroform, dichloroethane, chlorobenzene, dichlorobenzene, bromobenzene, aromatic nitro compounds such as nitrobenzene, acetic acid, propionic acid, monochloroacetic acid, fluoroacetic acid, trifluoroacetic acid and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid.
本発明において、反応温度は重要である。反応温度とし
ては４０〜１２０°Ｃの温度範囲が採用され、−
４０°Ｃ未満では十分な反応速度が得られず、１２０℃
を越えると副反応により４−クロロ−４゛−ヒドロキシ
ベンゾフェノンの収率が低下する。In the present invention, reaction temperature is important. A temperature range of 40 to 120°C is adopted as the reaction temperature; a sufficient reaction rate cannot be obtained below -40°C, and 120°C
If it exceeds this amount, the yield of 4-chloro-4'-hydroxybenzophenone decreases due to side reactions.
反応圧力は、本発明においては特に限定されるものでは
ないが、実用的には１０ ｋｇ ／ ｃｍ２以下、また
減圧下で行うこともできる。Although the reaction pressure is not particularly limited in the present invention, it is practically 10 kg/cm2 or less, and the reaction can also be carried out under reduced pressure.
反応時間は、本発明において特に限定されるものではな
いが、通常数分〜数十時間の反応時間が採用される。Although the reaction time is not particularly limited in the present invention, a reaction time of several minutes to several tens of hours is usually employed.
本発明において、反応装置は特に限定されるものではな
く、回分式、連続式及びこれらを組み合わせたものなど
が採用される。In the present invention, the reaction apparatus is not particularly limited, and a batch type, a continuous type, a combination thereof, etc. are employed.
［実施例１
次に、実施例によって本発明を更に具体的に説明するが
、本発明はその主旨を逸脱しない限りこれらの実施例に
よって限定されるものではない。[Example 1] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless it deviates from the spirit thereof.
実施例−１
３０００Ｃ四ツロフラスコに１０％ＮａＯＨ水溶液６０
ｍ１とフェノール１５ｇ （０，１６ｍｏｌ）を入れ室
温で撹拌する。そこへ、塩化パラクロロベンゾイル２５
ｇ （０，１４１０−
ｍｏｌ）を滴下する。生成した白色結晶を濾過し、その
結晶を水及びエタノールで洗浄した後、乾燥する。得ら
れた白色結晶をエタノールで再結晶することにより、は
ぼ純度１００％のパラクロロ安息香酸フェニルエステル
３０ｇ （１３ｍｏｌ）を得た。塩化パラクロロベンゾ
イル基準の収率は９３％であった。Example-1 10% NaOH aqueous solution 60°C in a 3000C four-way flask
Add m1 and 15 g (0.16 mol) of phenol and stir at room temperature. There, parachlorobenzoyl chloride 25
g (0,1410-mol) is added dropwise. The white crystals produced are filtered, washed with water and ethanol, and then dried. The obtained white crystals were recrystallized with ethanol to obtain 30 g (13 mol) of parachlorobenzoic acid phenyl ester with a purity of 100%. The yield based on parachlorobenzoyl chloride was 93%.
５０ｍ１フラスコに上記で合成したパラクロロ安息香酸
フェニルエステル１．０ｇ （４，３ｍｍｏｌ）、トリ
フルオロメタンスルホン酸５ｍｌを入れ、還流冷却器を
つけた後、撹拌しながら、４５〜５５°Ｃに昇温し、２
時間反応を行った。反応後、８ｍｍＨｇに減圧し、トリ
フルオロメタンスルホン酸を蒸留により回収した。Put 1.0 g (4.3 mmol) of parachlorobenzoic acid phenyl ester synthesized above and 5 ml of trifluoromethanesulfonic acid into a 50 ml flask, and after attaching a reflux condenser, raise the temperature to 45 to 55 °C while stirring. ,2
A time reaction was performed. After the reaction, the pressure was reduced to 8 mmHg, and trifluoromethanesulfonic acid was recovered by distillation.
得られた残渣に水１０ｍ１を加え、ついでジエチルエー
テルを加えることにより、生成物を有機層に抽出した。The product was extracted into an organic layer by adding 10 ml of water to the resulting residue and then adding diethyl ether.
有機層の分析を行ったところ、パラクロロ安息香酸フェ
ニルエステルの転化率は１００％でアリ、４−クロロ−
４゛−ヒドロキシベンゾフェノンが収率９３．９％、４
−クロロ−２′−ヒドロキシベンゾフェノンが収率６．
１％で得られた。パラｌオルト比は１５．４であった。Analysis of the organic layer revealed that the conversion rate of parachlorobenzoic acid phenyl ester was 100%.
4゛-Hydroxybenzophenone yield 93.9%, 4
-Chloro-2'-hydroxybenzophenone with a yield of 6.
Obtained at 1%. The para-ortho ratio was 15.4.
比較例−１
５０ｍ１フラスコにパラクロロ安息香酸１．６ｇ （１
０ｍｍｏｌ）、フェノール１．２ｇ （１３ｍｍｏｌ）
及びトリフルオロメタンスルホン酸５ｍｌを入れ、還流
冷却器を付けた後、撹拌しながら４５〜５５°Ｃに昇温
し、５時間反応をおこなった。反応後、実施例−１と同
様の処理をおこなったところ、パラクロロ安息香酸の転
化率は１００％であり、４−クロロ−４゛−ヒドロキシ
ベンゾフェノンが収率８８．９％、４−クロロ−２゛−
ヒドロキシベンゾフェノンが収率７．５％、パラクロロ
安息香酸フェニルエステルが収率３．５％で得られた。Comparative Example-1 1.6 g of parachlorobenzoic acid (1
0 mmol), phenol 1.2 g (13 mmol)
After adding 5 ml of trifluoromethanesulfonic acid and attaching a reflux condenser, the temperature was raised to 45 to 55°C with stirring, and reaction was carried out for 5 hours. After the reaction, the same treatment as in Example 1 was performed, and the conversion rate of parachlorobenzoic acid was 100%, and the yield of 4-chloro-4-hydroxybenzophenone was 88.9%, and 4-chloro-2゛-
Hydroxybenzophenone was obtained in a yield of 7.5%, and parachlorobenzoic acid phenyl ester was obtained in a yield of 3.5%.
パラｌオルト比は１１．９であった。The para-ortho ratio was 11.9.
実施例−２
実施例−１の方法において、反応温度を９０〜１００°
Ｃとし、その他は実施例−１と同様におこなった。Example-2 In the method of Example-1, the reaction temperature was set at 90 to 100°.
C, and the other procedures were the same as in Example-1.
パラクロロ安息香酸フェニルエステルの転化率は１００
％であり、４−クロロ−４゛−ヒドロキシベンゾフェノ
ンが収率９４．３％、４−クロロ−２′−ヒドロキシベ
ンゾフェノンが収率５．６％で得られた。パラｌオルト
比は１６．８であった。The conversion rate of parachlorobenzoic acid phenyl ester is 100
%, 4-chloro-4'-hydroxybenzophenone was obtained in a yield of 94.3%, and 4-chloro-2'-hydroxybenzophenone was obtained in a yield of 5.6%. The para-ortho ratio was 16.8.
［発明の効果］
本発明は、選択的に４−クロロ−４′−ヒドロキシベン
ゾフェノン類を製造する方法を提供するものである。し
かも、生成物とフルオロアルカンスルホン酸との分離は
容易であり、また、フルオロアルカンスルホン酸の再使
用も可能である。[Effects of the Invention] The present invention provides a method for selectively producing 4-chloro-4'-hydroxybenzophenones. Moreover, it is easy to separate the product from the fluoroalkanesulfonic acid, and the fluoroalkanesulfonic acid can also be reused.
得られた４−クロロ−４゛−ヒドロキシベンゾフェノン
類は、農薬、医薬等の原料または中間体として有用であ
る。また、本発明方法によれば純度の高い４−クロロ−
４゛−ヒドロキシベンゾフェノン類が得られるので、ポ
リエーテルケトン等の耐熱性ポリマーの原料または中間
体として特に有用である。The obtained 4-chloro-4'-hydroxybenzophenones are useful as raw materials or intermediates for agricultural chemicals, medicines, etc. Moreover, according to the method of the present invention, highly pure 4-chloro-
Since 4'-hydroxybenzophenones are obtained, it is particularly useful as a raw material or intermediate for heat-resistant polymers such as polyetherketone.
Claims (1)
ロロベンゾイル類をパラ位に置換基をもたないフェノー
ル類でエステル化して４−クロロ安息香酸フェニルエス
テルを得、単離し、次いで、その４−クロロ安息香酸フ
ェニルエステルをフルオロアルカンスルホン酸存在下、
４０〜１２０℃の温度範囲で反応させることを特徴とす
る４−クロロ−４−ヒドロキシベンゾフェノン類の製造
法。(1) 4-chlorobenzoic acid phenyl ester is obtained by esterifying parachlorobenzoic acids or halogenated parachlorobenzoyls with a phenol having no substituent at the para position, and isolating the 4-chlorobenzoic acid. Phenyl ester in the presence of fluoroalkanesulfonic acid,
A method for producing 4-chloro-4-hydroxybenzophenones, characterized by carrying out the reaction in a temperature range of 40 to 120°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1263411A JPH03127753A (en) | 1989-10-09 | 1989-10-09 | Production of 4-chloro-4'-hydroxybenzophenones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1263411A JPH03127753A (en) | 1989-10-09 | 1989-10-09 | Production of 4-chloro-4'-hydroxybenzophenones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03127753A true JPH03127753A (en) | 1991-05-30 |
Family
ID=17389124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1263411A Pending JPH03127753A (en) | 1989-10-09 | 1989-10-09 | Production of 4-chloro-4'-hydroxybenzophenones |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03127753A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006022904A3 (en) * | 2004-08-05 | 2006-12-28 | Arkema Inc | Removal of alkyl alkanesulfonate esters from alkanesulfonic acids and other organic media |
| US8471656B2 (en) | 2009-06-23 | 2013-06-25 | Panasonic Corporation | Electromagnetic relay |
| CN107778153A (en) * | 2016-08-31 | 2018-03-09 | 江苏万隆科技有限公司 | The preparation method of the dihydroxy benaophenonel of 4 chlorine 4 ' |
| CN107793303A (en) * | 2016-08-31 | 2018-03-13 | 江苏万隆科技有限公司 | The synthetic method of the dihydroxy benaophenonel of 4 chlorine 4 ' |
-
1989
- 1989-10-09 JP JP1263411A patent/JPH03127753A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006022904A3 (en) * | 2004-08-05 | 2006-12-28 | Arkema Inc | Removal of alkyl alkanesulfonate esters from alkanesulfonic acids and other organic media |
| US7297813B2 (en) | 2004-08-05 | 2007-11-20 | Arkema Inc. | Removal of alkyl alkanesulfonate esters from alkanesulfonic acids and other organic media |
| US8471656B2 (en) | 2009-06-23 | 2013-06-25 | Panasonic Corporation | Electromagnetic relay |
| US8912869B2 (en) | 2009-06-23 | 2014-12-16 | Panasonic Corporation | Electromagnetic relay |
| CN107778153A (en) * | 2016-08-31 | 2018-03-09 | 江苏万隆科技有限公司 | The preparation method of the dihydroxy benaophenonel of 4 chlorine 4 ' |
| CN107793303A (en) * | 2016-08-31 | 2018-03-13 | 江苏万隆科技有限公司 | The synthetic method of the dihydroxy benaophenonel of 4 chlorine 4 ' |
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