JPH0342256B2 - - Google Patents
Info
- Publication number
- JPH0342256B2 JPH0342256B2 JP60121950A JP12195085A JPH0342256B2 JP H0342256 B2 JPH0342256 B2 JP H0342256B2 JP 60121950 A JP60121950 A JP 60121950A JP 12195085 A JP12195085 A JP 12195085A JP H0342256 B2 JPH0342256 B2 JP H0342256B2
- Authority
- JP
- Japan
- Prior art keywords
- polyhydroxybenzophenone
- phosgene
- reaction
- tetrahydroxybenzophenone
- hydroxybenzene
- 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 - Lifetime
Links
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 14
- -1 zirconium halide Chemical class 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical group OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000005204 hydroxybenzenes Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 16
- 229960003742 phenol Drugs 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 229960001755 resorcinol Drugs 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000007664 blowing Methods 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
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- UQQYIAVMUUJWGX-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(3,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1 UQQYIAVMUUJWGX-UHFFFAOYSA-N 0.000 description 1
- CDCCEWISMXQKRI-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(3,5-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC(O)=CC(O)=C1 CDCCEWISMXQKRI-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WFVRYQQSGLPHGF-UHFFFAOYSA-N bis(2,3,4-trihydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O WFVRYQQSGLPHGF-UHFFFAOYSA-N 0.000 description 1
- UCJLQQGVBMWPGJ-UHFFFAOYSA-N bis(2,5-dihydroxyphenyl)methanone Chemical compound OC1=CC=C(O)C(C(=O)C=2C(=CC=C(O)C=2)O)=C1 UCJLQQGVBMWPGJ-UHFFFAOYSA-N 0.000 description 1
- TWOZFGMSWHUZKH-UHFFFAOYSA-N bis(2-hydroxy-4-octoxyphenyl)methanone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=C(OCCCCCCCC)C=C1O TWOZFGMSWHUZKH-UHFFFAOYSA-N 0.000 description 1
- XZXMWAHILBWKBI-UHFFFAOYSA-N bis(3,4-dihydroxyphenyl)methanone Chemical compound C1=C(O)C(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1 XZXMWAHILBWKBI-UHFFFAOYSA-N 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
- 230000005587 bubbling Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 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
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 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)
Description
〔産業上の利用分野〕
本発明はポリヒドロキシベンゾフエノンの製造
法に関する。さらに詳しくは、ヒドロキシベンゼ
ンとホスゲンとをハロゲン化ジルコニウム触媒の
存在下に反応せしめて、高収率で着色の少ないポ
リヒドロキシベンゾフエノンの製造法に関する。
2,2′,4,4′−テトラヒドロキシベンゾフエノ
ン、2,2′−ジヒドロキシ−4,4′−ジメトキシ
ベンゾフエノンなどのポリヒドロキシベンゾフエ
ノンは紫外線吸収剤としての利用等有用なもので
ある。
〔従来技術〕
従来、ポリヒドロキシベンゾフエノンの製造法
としては、例えば、米国特許第2854485号明細書、
同第2921962号明細書に示されるごとく、芳香族
カルボン酸とフエノールとを塩化亜鉛及び燐酸及
びオキシ塩化燐又は三塩化燐の存在下に反応させ
る方法が知られている。この米国特許の明細書に
は良好な収率でポリヒドロキシベンゾフエノンを
製造することができると記載されているけれども
本発明者らの経験によれば、この方法では高収率
でかつ着色の少ないポリヒドロキシベンゾフエノ
ンを得ることが難かしく、加えて、燐を含む排水
の処理に難点があり、ポリヒドロキシベンゾフエ
ノンの工業的製造法として満足できるものではな
かつた。
又、特開昭57−154140号公報には、芳香族カル
ボン酸とフエノールとをアルカンスルホン酸の存
在下に反応させる方法が開示されているが、使用
するアルカンスルホン酸が高価であるのに加え、
比較的高収率でポリヒドロキシベンゾフエノンを
得ようとすれば、芳香族カルボン酸1モルに対し
5モル以上のアルカンスルホン酸を使用しなけれ
ばならない。芳香族カルボン酸に対し、等モル程
度のアルカンスルホン酸の使用ではポリヒドロキ
シベンゾフエノンは、20%程度の収率でしか得ら
れないという欠点を有している。
又、ポリヒドロキシベンゾフエノンを得る他の
方法として、米国特許第2694729号明細書には、
レゾルシノールジメチルエーテルとホスゲンとを
塩化アルミニウムの存在下で、塩素化炭化水素を
溶媒にして反応させたのち、脱メチル化を行な
い、2,2′,4,4′−テトラヒドロキシベンゾフ
エノンを得る方法が開示されている。しかし該方
法では、収率が約35〜40%と低く、工業的に実施
するには、不適当である。
〔問題点を解決するための手段〕
本発明者らはこのような状況に鑑み、ポリヒド
ロキシベンゾフエノンの工業的製造法につき鋭意
検討を重ねた結果、ヒドロキシベンゼンとホスゲ
ンをハロゲン化ジルコニウム触媒の存在下に反応
せしめて高収率でかつ着色の少ないポリヒドロキ
シベンゾフエノンを得ることをみいだし、本発明
を完成させるにいたつた。すなわち本発明は一般
式
〔Rはアルキル基、アルコキシ基、ハロゲン原
子を表わし、Rが2以上(j≧2)の場合は同じ
置換基でも異なる置換基であつても良い。
iは1〜5の整数、jは0又は1〜4の整数で
ありi+j≦5である。〕
で表わされるヒドロキシベンゼンの1種又は2種
以上とホスゲンとをハロゲン化ジルコニウム触媒
の存在下に反応せしめて
〔Rはアルキル基、アルコキシ基、ハロゲン原
子を表わしRが2以上(n≧2及び又はq≧2)
の場合は同じ置換基でも異なる置換基であつても
良い。
m及びpは1〜5の整数、n及びqは0又は1
〜4の整数であり、m+n≦5及びp+q≦5で
ある。〕
で表わされるポリヒドロキシベンゾフエノンの製
造法である。
以下に本発明を詳述する。
本発明に用いられるヒドロキシベンゼンは、一
般式
〔式中Rはアルキル基、アルコキシ基、ハロゲ
ン原子を表わし、Rが2以上(j≧2)の場合は
同じ置換基でも異なる置換基であつても良い。i
は1〜5の整数、jは0又は1〜4の整数、i+
j≦5である〕
で示される化合物である。
Rはメチル基、エチル基、プロピル基、ブチル
基、オクチル基等の炭素数1〜12のアルキル基、
メトキシ基、エトキシ基、プロポキシ基、ブトキ
シ基、オクトキシ基等の炭素数1〜12のアルコキ
シ基、弗素、塩素、臭素、沃素等のハロゲン原子
が挙げられる。又jが2以上の整数を示す場合に
おいては、Rはそれぞれ同一種類の置換基であつ
ても異なる種類の置換基であつても良い。前記一
般式で表わされる化合物としては、例えばカテコ
ール、レゾルシン、ヒドロキノン、1,2,3−
トリヒドロキシベンゼン、レゾルシン−モノメチ
ルエーテル、レゾルシンモノオクテルエーテル、
3,5−ジヒドロキシトルエン等が挙げられる。
本発明の反応生成物は一般式
(R,m,p,q及びm+n,p+qは上記定
業と同じである。)
で示されるポリヒドロキシベンゾフエノンであ
り、原料として用いる前記ヒドロキシベンゼンに
対応した化合物である。
このようなポリヒドロキシベンゾフエノンとし
ては、3,3′,4,4′−テトラヒドロキシベンゾ
フエノン、2,2′,4,4′−テトラヒドロキシベ
ンゾフエノン、2,2′,5,5′−テトラヒドロキ
シベンゾフエノン、2,2′,3,3′,4,4′−ヘ
キサヒドロキシベンゾフエノン、2,2′−ジヒド
ロキシ−4,4′−ジメトキシベンゾフエノン、
2,2′−ジヒドロキシ−4,4′−ジオクトキシベ
ンゾフエノン、2,3′,4,4′−テトラヒドロキ
シベンゾフエノン、2,2′,4,4′−テトラヒド
ロキシベンゾフエノン、2,3′,4,5′−テトラ
ヒドロキシベンゾフエノン等が挙げられる。
ヒドロキシベンゼンとホスゲンは一般には溶媒
の存在下に反応せしめる。
ヒドロキシベンゼンとハロゲン化ジルコニウム
を溶媒に溶解又は懸濁させた状態下、ホスゲンを
吹き込んで反応させる方法が採用される。又、溶
媒にヒドロキシベンゼンとハロゲン化ジルコニウ
ム、ホスゲンをあらかじめ、約0〜10℃といつた
低温で溶解又は懸濁させておき、昇温させながら
反応させることもできる。
溶媒としては、二硫化炭素、ニトロベンゼン、
1,2−ジクロルエタン、クロルベンゼン、ブロ
モベンゼン、O−ジクロベンゼン、m−ジクロル
ベンゼンなどを用いることができる。なかでも、
ニトロベンゼンは、極性大であり、ヒドロキシベ
ンゼン、ハロゲン化ジルコニウムを容易に溶解せ
しめる為溶媒として、好ましい。
ヒドロキシベンゼン、溶媒、ハロゲン化ジルコ
ニウム、ホスゲンの使用量については、目的物の
種類、反応方法などの違いにより異なり一概に規
定できないが、一般にヒドロキシベンゼンは溶媒
に約3〜40重量%の割合に仕込み、ホスゲンの使
用量は、ヒドロキシベンゼンに対し、理論量の約
0.5〜8倍モル、好ましくは、約1〜4倍モル、
ハロゲン化ジルコニウムをヒドロキシベンゼン1
モルに対し、約0.1〜4倍モル好ましくは、約0.2
〜2倍モル添加される。溶媒中のヒドロキシベン
ゼンの濃度が約40重量%をこえると、副生成物の
生成割合が増加するし、一方濃度が低くなると、
生産性が悪くなる為一般に約3〜40重量%好まし
くは約7〜20重量%で反応させる。又、ホスゲン
は多く使用してもそれに見合つた効果が得られな
いので、一般には、約0.5〜8倍モル、好ましく
は約1〜4倍モル用いられる。ハロゲン化ジルコ
ニウムの使用量が約4倍モルをこえると、副生成
物の増加が著しくなるし、一方約0.1倍モルより
少ない場合には、反応が充分進行しない為好まし
くない。
反応温度は、約0〜120℃好ましくは約30〜90
℃で実施される。好適な温度範囲以上になれば、
副生成物の増加が著しくなり、一方好適な温度範
囲以下では、反応の完結に長時間を要する様にな
る。
ホスゲンの吹き込み時間あるいは滴下時間につ
いては、吹き込みあるいは滴下によつて、異常に
発熱しない範囲であれば良い。
ホスゲンの導入後、反応完結の為に約1〜20時
間の熟成時間を設けることは効果的である。
反応温度、反応時間又は触媒量など反応条件に
よつては中間体と思われるヒドロキシベンゾエー
トも得られる。
反応によつて生成したポリヒドロキシベンゾフ
エノンは、反応生成物中に冷水を滴下するか、生
成物を、冷水中に投入し、析出したポリヒドロキ
シベンゾフエノンを過、水洗、再結晶等の通常
の分離精製法により分離製して、目的の着色の少
ないポリヒドロキシベンゾフエノンを得ることが
できる。
〔発明の効果〕
以上詳述した本発明方法によれば2,2′,4,
4′−テトラヒドロキシベンゾフエノンの場合、従
来公知の方法の35−40%という収率に比して約60
〜80%という著しく高収率で着色の少ないポリヒ
ドロキシベンゾフエノンを製造することができ、
その工業的価値は極めて大きい。
〔実施例〕
以下に本発明方法を実施例により説明するが、
本発明方法はこれらの実施例によつて制限される
ものではない。
実施例 1
ニトロベンゼン1Kg、レゾルシン110g、塩化
ジルコニウム58gを24つ口フラスコに仕込み
フラスコ内をN2ガスで置換後70℃まで昇温した。
次いでホスゲンを99g、5時間かけて温度を70℃
に維持しながら、撹拌下に吹き込んだ後4時間熟
成した。熟成終了後反応生成物を水冷し、水500
g滴下し、撹拌下、1時間放置後生成物を過、
水洗し、152gの黄かつ色のウエツトケーキを得
た。ウエツトケーキを熱水に溶解、冷却再結晶し
て乾燥したところ、着色の少い2,2′,4,4′−
テトラヒドロキシベンゾフエノン91gが得られ
た。レゾルシンの転化率は85%であり、2,2′,
4,4′−テトラヒドロキシベンゾフエノンの収率
は74%であつた。
塩化ジルコニウムにかえ、臭化ジルコニウム
100gを用いた以外は上記と同様に反応させた。
その結果、着色の少ない2,2′,4,4′−テトラ
ヒドロキシベンゾフエノンの収率は71%であつ
た。
比較例 1〜8
ハロゲン化ジルコニウムを、表1に示す金属塩
化物にかえた以外は実施例1と同様に反応を行な
つた。金属塩化物の量はレゾルシン1モルに対し
0.5モルの割合で仕込んだ。結果を表1に示す。
[Industrial Field of Application] The present invention relates to a method for producing polyhydroxybenzophenone. More specifically, the present invention relates to a method for producing polyhydroxybenzophenone with high yield and little coloring by reacting hydroxybenzene and phosgene in the presence of a halogenated zirconium catalyst.
Polyhydroxybenzophenones such as 2,2',4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone are useful as ultraviolet absorbers. It is. [Prior Art] Conventionally, methods for producing polyhydroxybenzophenone include, for example, US Pat. No. 2,854,485;
As shown in the specification of the same No. 2921962, a method is known in which an aromatic carboxylic acid and a phenol are reacted in the presence of zinc chloride, phosphoric acid, and phosphorus oxychloride or phosphorus trichloride. Although the specification of this US patent states that polyhydroxybenzophenone can be produced in good yield, according to the experience of the present inventors, this method can produce polyhydroxybenzophenone in high yield and without coloring. It is difficult to obtain a small amount of polyhydroxybenzophenone, and in addition, there are difficulties in treating wastewater containing phosphorus, and this method has not been satisfactory as an industrial method for producing polyhydroxybenzophenone. Furthermore, JP-A-57-154140 discloses a method of reacting aromatic carboxylic acid and phenol in the presence of alkanesulfonic acid, but in addition to the fact that the alkanesulfonic acid used is expensive, ,
In order to obtain polyhydroxybenzophenone in a relatively high yield, it is necessary to use 5 or more moles of alkanesulfonic acid per mole of aromatic carboxylic acid. When using an equimolar amount of alkanesulfonic acid with respect to aromatic carboxylic acid, polyhydroxybenzophenone has the disadvantage that a yield of only about 20% can be obtained. In addition, as another method for obtaining polyhydroxybenzophenone, US Pat. No. 2,694,729 describes
A method of reacting resorcinol dimethyl ether and phosgene in the presence of aluminum chloride using a chlorinated hydrocarbon as a solvent, followed by demethylation to obtain 2,2',4,4'-tetrahydroxybenzophenone. is disclosed. However, this method has a low yield of about 35 to 40%, making it unsuitable for industrial implementation. [Means for Solving the Problems] In view of the above circumstances, the present inventors have conducted intensive studies on the industrial production method of polyhydroxybenzophenone. The present inventors have discovered that polyhydroxybenzophenone can be obtained in high yield and with little coloration by reacting in the presence of polyhydroxybenzophenone, leading to the completion of the present invention. That is, the present invention is based on the general formula [R represents an alkyl group, an alkoxy group, or a halogen atom, and when R is 2 or more (j≧2), they may be the same or different substituents. i is an integer of 1 to 5, j is 0 or an integer of 1 to 4, and i+j≦5. ] One or more hydroxybenzenes represented by the following are reacted with phosgene in the presence of a halogenated zirconium catalyst. [R represents an alkyl group, an alkoxy group, or a halogen atom, and R is 2 or more (n≧2 and or q≧2)
In the case of , the substituents may be the same or different. m and p are integers of 1 to 5, n and q are 0 or 1
It is an integer of ~4, m+n≦5 and p+q≦5. ] This is a method for producing polyhydroxybenzophenone represented by: The present invention will be explained in detail below. Hydroxybenzene used in the present invention has the general formula [In the formula, R represents an alkyl group, an alkoxy group, or a halogen atom, and when R is 2 or more (j≧2), they may be the same substituent or different substituents. i
is an integer of 1 to 5, j is 0 or an integer of 1 to 4, i+
j≦5]. R is an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group,
Examples thereof include alkoxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, and octoxy group, and halogen atoms such as fluorine, chlorine, bromine, and iodine. Further, when j represents an integer of 2 or more, R may be the same type of substituent or different types of substituents. Examples of the compound represented by the above general formula include catechol, resorcinol, hydroquinone, 1,2,3-
Trihydroxybenzene, resorcin monomethyl ether, resorcin monooctele ether,
Examples include 3,5-dihydroxytoluene. The reaction product of the present invention has the general formula (R, m, p, q and m+n, p+q are the same as the above-mentioned formula.) It is a polyhydroxybenzophenone represented by the following and is a compound corresponding to the above-mentioned hydroxybenzene used as a raw material. Such polyhydroxybenzophenones include 3,3',4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2',5, 5'-tetrahydroxybenzophenone, 2,2',3,3',4,4'-hexahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxy-4,4'-dioctoxybenzophenone, 2,3',4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone , 2,3',4,5'-tetrahydroxybenzophenone and the like. Hydroxybenzene and phosgene are generally reacted in the presence of a solvent. A method is adopted in which hydroxybenzene and zirconium halide are dissolved or suspended in a solvent, and phosgene is blown into the solution to react. Alternatively, hydroxybenzene, zirconium halide, and phosgene can be dissolved or suspended in a solvent at a low temperature of about 0 to 10°C in advance, and the reaction can be carried out while raising the temperature. As a solvent, carbon disulfide, nitrobenzene,
1,2-dichloroethane, chlorobenzene, bromobenzene, O-dichlorobenzene, m-dichlorobenzene, etc. can be used. Among them,
Nitrobenzene is highly polar and is preferred as a solvent because it easily dissolves hydroxybenzene and zirconium halide. The amounts of hydroxybenzene, solvent, zirconium halide, and phosgene to be used vary depending on the type of target product, reaction method, etc., and cannot be unconditionally defined, but in general, hydroxybenzene is added to the solvent at a ratio of about 3 to 40% by weight. , the amount of phosgene used is approximately the theoretical amount for hydroxybenzene.
0.5 to 8 times the mole, preferably about 1 to 4 times the mole,
Zirconium halide with hydroxybenzene 1
About 0.1 to 4 times the mole, preferably about 0.2
~2 times the mole amount is added. When the concentration of hydroxybenzene in the solvent exceeds about 40% by weight, the proportion of by-products produced increases, while when the concentration decreases,
Since productivity deteriorates, the reaction is generally carried out at about 3 to 40% by weight, preferably about 7 to 20% by weight. Further, even if a large amount of phosgene is used, a commensurate effect cannot be obtained, so it is generally used in about 0.5 to 8 times the molar amount, preferably about 1 to 4 times the molar amount. When the amount of zirconium halide used exceeds about 4 times the mole, the amount of by-products increases significantly, while when it is less than about 0.1 times the mole, the reaction does not proceed sufficiently, which is not preferable. The reaction temperature is about 0 to 120°C, preferably about 30 to 90°C.
Conducted at °C. If the temperature exceeds the suitable range,
The increase in by-products becomes significant, and on the other hand, below the preferred temperature range, it takes a long time to complete the reaction. The time for blowing or dropping phosgene may be within a range that does not cause abnormal heat generation due to blowing or dropping. After the introduction of phosgene, it is effective to provide an aging time of about 1 to 20 hours to complete the reaction. Hydroxybenzoate, which is considered to be an intermediate, can also be obtained depending on reaction conditions such as reaction temperature, reaction time, and catalyst amount. The polyhydroxybenzophenone produced by the reaction can be prepared by dropping cold water into the reaction product or by pouring the product into cold water and filtering, washing with water, recrystallizing the precipitated polyhydroxybenzophenone, etc. The target polyhydroxybenzophenone with less coloring can be obtained by separating and producing it by a conventional separation and purification method. [Effect of the invention] According to the method of the present invention detailed above, 2, 2', 4,
In the case of 4'-tetrahydroxybenzophenone, the yield was about 60% compared to the 35-40% yield of the conventionally known method.
It is possible to produce polyhydroxybenzophenone with extremely high yield of ~80% and less coloring.
Its industrial value is extremely large. [Example] The method of the present invention will be explained below using Examples.
The method of the invention is not limited to these examples. Example 1 1 kg of nitrobenzene, 110 g of resorcinol, and 58 g of zirconium chloride were placed in a 24-necked flask, and the inside of the flask was purged with N 2 gas, and then the temperature was raised to 70°C.
Next, 99g of phosgene was added to the temperature at 70°C over 5 hours.
The mixture was aged for 4 hours after bubbling while stirring. After aging, the reaction product is cooled with water and 500 ml of water is added.
g dropwise, and after standing for 1 hour under stirring, filter the product.
After washing with water, 152 g of a yellow wet cake was obtained. When the wet cake was dissolved in hot water, cooled, recrystallized, and dried, 2,2',4,4'-
91 g of tetrahydroxybenzophenone were obtained. The conversion rate of resorcinol was 85%, and 2,2′,
The yield of 4,4'-tetrahydroxybenzophenone was 74%. Zirconium bromide instead of zirconium chloride
The reaction was carried out in the same manner as above except that 100 g was used.
As a result, the yield of 2,2',4,4'-tetrahydroxybenzophenone with little coloring was 71%. Comparative Examples 1 to 8 The reaction was carried out in the same manner as in Example 1, except that the zirconium halide was changed to the metal chloride shown in Table 1. The amount of metal chloride is per mole of resorcinol.
It was prepared at a ratio of 0.5 mol. The results are shown in Table 1.
【表】
ゾフエノン
実施例 2
ニトロベンゼン600g、レゾルシンモノメチル
エーテル45g、塩化ジルコニウム42gを1の四
つ口フラスコに仕込み、フラスコ内をN2ガスで
置換した後70℃まで昇温した。次いでホスゲンを
36g、2時間かけて温度を70℃に維持しながら撹
拌して吹き込んだ後4時間熟成した。水冷の後約
200gの水を滴下し、撹拌下1時間放置した。分
離したニトロベンゼン層に15%NaOH水溶液を
200g加え、反応生成物を抽出し15%HClで中和
して、生成物を析出させた。析出物を過水洗
し、乾燥したところ、着色の少い2,2′−ジヒド
ロキシ−4,4′−ジメトキシベンゾフエノン(m.
p.137〜138゜)を28g得た。収率は56%であつた。[Table] Zophenone Example 2 600 g of nitrobenzene, 45 g of resorcinol monomethyl ether, and 42 g of zirconium chloride were placed in the four-necked flask in step 1, and after purging the inside of the flask with N 2 gas, the temperature was raised to 70°C. Then phosgene
36g was poured into the solution over 2 hours with stirring while maintaining the temperature at 70°C, and then aged for 4 hours. After water cooling approx.
200 g of water was added dropwise, and the mixture was left stirring for 1 hour. Add 15% NaOH aqueous solution to the separated nitrobenzene layer.
200 g was added, and the reaction product was extracted and neutralized with 15% HCl to precipitate the product. When the precipitate was washed with water and dried, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (m.
137-138°) was obtained. The yield was 56%.
Claims (1)
数、jは0または1の整数である。〕 で表されるヒドロキシベンゼンの1種又は2種以
上とホスゲンとをハロゲン化ジルコニウム触媒の
存在下に反応せしめて 一般式 〔Rはアルコキシ基を表し、m及びpは1〜2
の整数、n及びqは0又は1の整数である。〕 で表されるポリヒドロキシベンゾフエノンの製造
法。 2 ポリヒドロキシベンゾフエノンが で表される2,2′,4,4′−テトラヒドロキシベ
ンゾフエノンであることを特徴とする特許請求の
範囲第1項記載のポリヒドロキシベンゾフエノン
の製造法。[Claims] 1. General formula [R represents an alkoxy group, i is an integer of 1 to 2, and j is an integer of 0 or 1. ] One or more hydroxybenzenes represented by the formula are reacted with phosgene in the presence of a zirconium halide catalyst to form a compound of the general formula [R represents an alkoxy group, m and p are 1-2
, n and q are integers of 0 or 1. ] A method for producing polyhydroxybenzophenone represented by: 2 Polyhydroxybenzophenone is The method for producing polyhydroxybenzophenone according to claim 1, wherein the polyhydroxybenzophenone is 2,2',4,4'-tetrahydroxybenzophenone represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60121950A JPS61293946A (en) | 1985-06-05 | 1985-06-05 | Production of polyhydroxybenzophenone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60121950A JPS61293946A (en) | 1985-06-05 | 1985-06-05 | Production of polyhydroxybenzophenone |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61293946A JPS61293946A (en) | 1986-12-24 |
JPH0342256B2 true JPH0342256B2 (en) | 1991-06-26 |
Family
ID=14823928
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60121950A Granted JPS61293946A (en) | 1985-06-05 | 1985-06-05 | Production of polyhydroxybenzophenone |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61293946A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60208938A (en) * | 1983-12-22 | 1985-10-21 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Manufacture of benzophenone |
-
1985
- 1985-06-05 JP JP60121950A patent/JPS61293946A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60208938A (en) * | 1983-12-22 | 1985-10-21 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Manufacture of benzophenone |
Also Published As
Publication number | Publication date |
---|---|
JPS61293946A (en) | 1986-12-24 |
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