JPH02255634A - Production of 4,4'''-dihydroxyquaterphenyl or its derivative - Google Patents
Production of 4,4'''-dihydroxyquaterphenyl or its derivativeInfo
- Publication number
- JPH02255634A JPH02255634A JP1075173A JP7517389A JPH02255634A JP H02255634 A JPH02255634 A JP H02255634A JP 1075173 A JP1075173 A JP 1075173A JP 7517389 A JP7517389 A JP 7517389A JP H02255634 A JPH02255634 A JP H02255634A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- general formula
- hydroxy
- pref
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- DYOVJPZEQNDPPZ-UHFFFAOYSA-N 4-[2-[2-(4-hydroxyphenyl)phenyl]phenyl]phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1C1=CC=CC=C1C1=CC=C(O)C=C1 DYOVJPZEQNDPPZ-UHFFFAOYSA-N 0.000 title claims 3
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 230000000447 dimerizing effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 6
- 238000006471 dimerization reaction Methods 0.000 abstract description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 150000004679 hydroxides Chemical class 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 238000005695 dehalogenation reaction Methods 0.000 abstract 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 4
- 238000003916 acid precipitation Methods 0.000 description 4
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WGPAQYSVWYWZKT-UHFFFAOYSA-N [C].[Ra] Chemical compound [C].[Ra] WGPAQYSVWYWZKT-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- USYQKCQEVBFJRP-UHFFFAOYSA-N 1-bromo-3-phenylbenzene Chemical group BrC1=CC=CC(C=2C=CC=CC=2)=C1 USYQKCQEVBFJRP-UHFFFAOYSA-N 0.000 description 1
- CMYZTJCWFRFRIW-UHFFFAOYSA-N 1-bromo-4-(4-methoxyphenyl)benzene Chemical group C1=CC(OC)=CC=C1C1=CC=C(Br)C=C1 CMYZTJCWFRFRIW-UHFFFAOYSA-N 0.000 description 1
- ZGOWIHIGUHWAMQ-UHFFFAOYSA-N 2-(4-bromophenyl)phenol Chemical group OC1=CC=CC=C1C1=CC=C(Br)C=C1 ZGOWIHIGUHWAMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- HYERMANNZHVNLP-UHFFFAOYSA-N OC=1C(=C(C=CC=1)C=1C(=CC=CC=1)C=1C(=CC=CC=1)C1=CC=CC=C1)O Chemical group OC=1C(=C(C=CC=1)C=1C(=CC=CC=1)C=1C(=CC=CC=1)C1=CC=CC=C1)O HYERMANNZHVNLP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000005947 deacylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- -1 gulonol Chemical compound 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、一般式ＣＩ）
〔一般式（Ｉ）で、Ｒは水素原子、アルキル基又はアシ
ル基を示す。〕
で表わされる４、４／ＩＩ−ジヒドロキシクォーターフ
ェニル又はその誘導体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a compound of the general formula CI) [In the general formula (I), R represents a hydrogen atom, an alkyl group, or an acyl group. ] It is related with the manufacturing method of 4,4/II-dihydroxyquaterphenyl or its derivative represented by these.
一般式（りで表わされる化合物は各種工業原料、特に液
晶表示素子の液晶化合物や耐熱性高分子化合物、合成が
ム改質剤等の原料としてその有用性が大きく期待されて
いる。Compounds represented by the general formula (R) are highly expected to be useful as raw materials for various industrial raw materials, particularly for liquid crystal compounds for liquid crystal display devices, heat-resistant polymer compounds, and synthetic modifiers.
これらの化合物の製造方法としては次の方法が提案され
ている。The following methods have been proposed as methods for producing these compounds.
（１） ４’−ヨード−４−メトキシピフェニルヲ多
量の鋼合金の共存下に窒素雰囲気中で２８０℃に加熱し
、脱ヨード化二量体化する方法。(1) A method of deiodinating and dimerizing 4'-iodo-4-methoxypiphenyl by heating it to 280° C. in a nitrogen atmosphere in the coexistence of a large amount of a steel alloy.
（２） ４’−ブロム−４−メトキシピフェニルをエ
ーテル溶媒中でマグネシウム及び臭化エチルと反応せし
めたのち、塩化鋼を加えて加熱し、二量体化する方法〔
上記の（１）及び（２）の方法は例えば工ＣＳ、。(2) A method in which 4'-bromo-4-methoxypiphenyl is reacted with magnesium and ethyl bromide in an ether solvent, and then chlorinated steel is added and heated to dimerize [
Methods (1) and (2) above include, for example, engineering CS.
１９４０、ｐｐ、１３７９〜１３８２に開示されている
〕。1940, pp. 1379-1382].
しかしながら、いづれも多量の調合金粉やマグネシウム
金属粉を必要とし、また反応条件が苛酷であったり、安
全上、衛生上或いは公害防止上の問題が多く、しかも目
的物の収率も満足できるものではない。However, all of these require large amounts of prepared alloy powder and magnesium metal powder, the reaction conditions are harsh, there are many safety, hygiene, and pollution prevention problems, and the yield of the target product is not satisfactory. do not have.
（３） なお４− ｂｒｏｍｏｂｉｐｈ＠ｓｙｅを３
２ ’Ａ ｍｅｄｉｕｍｈｙｄｒｏｘｉｄｅ水溶液中で
ｓｏｄｉｕｍ ｆｏｒｍａｔ＠、ｐａｌｌａｄｌｕｍｏ
ｎ ｃｈａｒｃｏａｌ及び５ｕｒｆａｃｔａｎｔ の
共存下で二量体化せしめる方法（５ｙｎｔｈ＠ｓｉｓ
、 Ｊｕｌｙ ＊ １９７８ ＊ｐ、 ５３８． Ｔａ
ｂｌｅ ）が開示されているが、これは核置換基を有し
ないｐ−ｑｕａｔ＠ｒｐｈ＠ｎ７・２の製造方法であり
、４−位及び４ｍ−位に置換基を有する本発明の目的物
とは異なシ、又その収率も４８係と満足すべきものでは
ない。(3) Note that 4-bromobiph@sye is 3
2'A medium hydroxide aqueous solution in sodium format@, palladlumo
A method of dimerization in the coexistence of n charcoal and 5urfactant (5ynth@sis
, July * 1978 *p, 538. Ta
ble) is disclosed, which is a method for producing p-quat@[email protected] that does not have a nuclear substituent, and does not contain the object of the present invention that has substituents at the 4- and 4m-positions. The yield was 48%, which is not satisfactory.
（４）又、４− ｂｒｏｍｏｂｉｐｈ＠ｎｙｓを、１０
％ ｓｏｄｉｕｍｈｙｄｒｏｘｉｄｅ水溶液中で、ｐ
ａｌｌａｄｌｕｍ ｏｎ ｃｈａｒｃｏａｌ及びｈ＊ｘ
ａｄ＠ａｙｌ ｔｒｉｍ＊ｔｈｙｌ ｍｍｍｏｎｉｕｍ
ｂｒｏｍｉｄｅの共存下、ｃａｒｂｏｎ ｍｏｎｏｘ
ｉｄ・加圧下で二量体化せしめる方法（ＥＰ ０２０６
５４３、ｃｏｌｕｍｎ １４．Ｅｘａｍｐｌｅ１５）が
開示されているが、これも前記と同じく核置換基を有し
ないｐ −ｑｕａｔ・ｒｐｈ・ｎｙｌの製造方法であフ
、転化率は１０ｅｓと極めて低い。(4) Also, 4-bromobiph@nys, 10
% sodium hydroxide aqueous solution, p
alladlum on charcoal and h*x
ad@ayl trim*thyl mmmonium
Carbon monox in the coexistence of bromide
id/method of dimerization under pressure (EP 0206
543, column 14. Example 15) is disclosed, but like the above, this is also a method for producing p-quat.rph.nyl without a nuclear substituent, and the conversion rate is extremely low at 10es.
本発明者らは従来技術のかかる問題点を解決するため種
々検討を重ねた結果、特殊な薬品類や装置、操作を必要
とせず、安全、衛生及び公害防止上からも何ら問題を生
ずる恐れなく、かつ高品質の目的物を高収率で製造でき
る方法に到達した。The inventors of the present invention have conducted various studies in order to solve the problems of the prior art, and have found that there is no need for special chemicals, equipment, or operation, and there is no risk of causing any problems in terms of safety, hygiene, and pollution prevention. We have achieved a method that can produce high-quality target products with high yields.
すなわち本発明の製造方法は、一般式（Ｉ［）〔一般式
（ＩＩ）で、Ｒは水素原子、アルキル基又はアシル基を
、Ｘはハロダン原子をそれぞれ示す。〕で表わされる４
−ヒドロキシ−４′−ハＥｌｙノビフェニル又はその誘
導体を、不活性有機極性溶媒中で、アルカリ金属又はア
ルカリ土類金属の水酸化物、炭酸塩或いは重炭酸塩の１
種又は２種以上の共存下に、ツクラジウムを触媒として
、脱ハロダン化二量化することを特徴とする。That is, the production method of the present invention is based on the general formula (I[) [general formula (II)], where R represents a hydrogen atom, an alkyl group, or an acyl group, and X represents a halodane atom. ] 4
-Hydroxy-4'-Elynobiphenyl or a derivative thereof is dissolved in an alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate in an inert organic polar solvent.
It is characterized by dehalodanization and dimerization in the presence of one species or two or more species using Tsucladium as a catalyst.
本発明についてさらに詳細に説明する。The present invention will be explained in more detail.
一般式（Ｉｆ）で表わされる化合物の具体例としては、
４−ヒドロキシ−４７−ヨードピフェニル、４−ヒドロ
キシ−４７−クロルピフェニル、４−ヒドロキシ−４′
−ブロム−ピフェニル及びこレラの化合物の４−ヒドロ
キシル基のアセトキシル化、ベンゾイルオキシ化、メチ
ルエーテル化、エチルエーテル化誘導体等が挙げられる
。工業的にはその製造時における安全衛生上の問題や収
率、品質などの点及び本発明方法における後処理の問題
等から、４−ヒドロキシ−４７−ブロムビフェニル又ハ
４−アセトキシ−４′−ブロムピフェニルが好マシい。Specific examples of the compound represented by the general formula (If) include:
4-hydroxy-47-iodopiphenyl, 4-hydroxy-47-chlorpiphenyl, 4-hydroxy-4'
Examples include acetoxylation, benzoyloxylation, methyl etherification, and ethyl etherification derivatives of the 4-hydroxyl group of -bromo-piphenyl and cholera compounds. Industrially, 4-hydroxy-47-brombiphenyl or 4-acetoxy-4'- Brompiphenyl is better.
不活性有機活性溶媒としては、メタノール、エタノール
、グロノぐノール、ブタノール等のアルコール類、エチ
レングリコール、プロピレングリコール、グリセリン等
のグ°リコール類又はそれらの低級アルキルエーテル類
等が例挙されるが、メタノール、エタノール、エチレン
グリコール等が好ましい。その使用量は一般式（Ｉｆ）
の化合物の１〜１０重量倍、好ましくは１．５〜３倍量
である。なお、本発明ではこの不活性有機活性溶媒を水
と混合して用いることもできる。Examples of inert organic solvents include alcohols such as methanol, ethanol, gulonol, butanol, glycols such as ethylene glycol, propylene glycol, and glycerin, and lower alkyl ethers thereof. Methanol, ethanol, ethylene glycol and the like are preferred. The amount used is the general formula (If)
The amount is 1 to 10 times by weight, preferably 1.5 to 3 times the weight of the compound. In addition, in the present invention, this inert organic active solvent can also be used in combination with water.
アルカリ金属又はアルカリ土類金属の水酸化物、炭酸塩
或いは重炭酸塩としては、Ｎａ 、 Ｋ 、 Ｍｇ 。Examples of hydroxides, carbonates, and bicarbonates of alkali metals or alkaline earth metals include Na, K, and Mg.
Ｃａ 、 Ｚｎ 、 Ｂａ等の水酸化物、炭酸塩或いは
重炭酸塩が例挙されるが、好ましいのは水酸化ナトリウ
ム又は水酸化カリウムである。これらは微粉体又は水溶
液として用いられるが、逸常１〜５０重量係、特に５〜
２０重量幅の水溶液として使用するのが好ましい。Examples include hydroxides, carbonates, and bicarbonates of Ca, Zn, Ba, etc., but sodium hydroxide or potassium hydroxide is preferred. These are used as fine powders or aqueous solutions, but they are usually 1 to 50% by weight, especially 5 to 50% by weight.
Preferably, it is used as a 20 weight range aqueous solution.
触媒のノＪ？ラジウムは活性炭、シリカ、アルミナ、シ
リカ−アルミナ、珪藻土、ゼオライト、炭酸カルシウム
、炭酸ストロンチウム、硫酸ノ々リウム等に担持させた
ものが適当である。パラジウムの担体に対する担持量は
０．１〜２０重量係、好ましくは０．５〜１０重量俤で
ある。その使用量は一般式（ｆｆ）の化合物１モルに対
して触媒金属原子換算で０．０１〜１００ミリモル、好
ましくは１〜５０ミリモル相当量である。触媒は反応終
了後分離回収して、反応に反覆使用が可能であるが、触
媒活性が低下した場合には、常法によ〕触媒（担体共に
）を焼成、還元賦活すればほとんど初使用時の活性に復
活することが出来る。従りて触媒は取シ扱い損失を極力
防止すればコスト的には大きな負担とはならない。Catalyst no J? Suitable radiums are those supported on activated carbon, silica, alumina, silica-alumina, diatomaceous earth, zeolite, calcium carbonate, strontium carbonate, norium sulfate, and the like. The amount of palladium supported on the carrier is 0.1 to 20% by weight, preferably 0.5 to 10% by weight. The amount used is 0.01 to 100 mmol, preferably 1 to 50 mmol, in terms of catalytic metal atoms, per 1 mole of the compound of general formula (ff). The catalyst can be separated and recovered after the reaction and used repeatedly in the reaction, but if the catalyst activity decreases, the catalyst (together with the support) can be fired and reactivated using a conventional method, and the catalyst can be used for the first time. can be revived to its active state. Therefore, if the handling loss of the catalyst is avoided as much as possible, the cost will not be large.
反応温度、時間は上記各種反応条件によりて適当に選択
されるが、通常反応温度は５０〜２００℃、好ましくは
８０〜１５０℃であり、反応時間は１〜１２時間、通常
２〜６時間である。The reaction temperature and time are appropriately selected depending on the above various reaction conditions, but the reaction temperature is usually 50 to 200°C, preferably 80 to 150°C, and the reaction time is 1 to 12 hours, usually 2 to 6 hours. be.
反応は溶媒の種類及び反応温度によシ常圧又は加圧下で
行なうことが出来る。反応雰囲気は不活性ガスや還元性
ガス置換の必要はない。The reaction can be carried out under normal pressure or elevated pressure depending on the type of solvent and reaction temperature. There is no need to replace the reaction atmosphere with an inert gas or reducing gas.
反応終了後、室温で反応混合物を濾過して目的物（塩）
及び触媒の混合物ｔＦ取し、非プロトン性極性溶媒、例
えばＮ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチル
アセトアミド、１，３−ジメチル−２−イミダゾリジノ
ン等を加えて目的物を溶解し触媒を分離回収する。目的
物の極性溶媒溶液は希硫酸、希塩酸等で酸析して、Ｐ取
する。又は反応混合物に希硫酸、希塩酸等を加えて目的
物（塩）を遊離化したのち濾過して、目的物及び触媒の
混合物を分離し、これを非プロトン性極性溶媒を加えて
加熱し、目的物のみを溶解して触媒を一過分離し、Ｐ液
を冷却して目的物を晶出させ、回収することも出来る。After the reaction is complete, filter the reaction mixture at room temperature to remove the target product (salt).
A mixture of tF and catalyst is taken, an aprotic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, etc. is added to dissolve the target substance, and the catalyst is dissolved. Separate and collect. A solution of the target product in a polar solvent is acid-precipitated with dilute sulfuric acid, dilute hydrochloric acid, etc. to remove P. Alternatively, add dilute sulfuric acid, dilute hydrochloric acid, etc. to the reaction mixture to liberate the target product (salt), filter it to separate a mixture of the target product and catalyst, add an aprotic polar solvent and heat it, and release the target product (salt). It is also possible to dissolve only the substance, temporarily separate the catalyst, cool the P liquid, crystallize the target substance, and recover it.
この回収母液又は前記酸析母液から目的物又は原料（又
はその脱ハロゲン化物）が回収される。The target product or raw material (or its dehalogenated product) is recovered from this recovered mother liquor or the acid precipitation mother liquor.
このようにして得られた目的物は必要に応じ再結晶等に
よシ精製される。The target product thus obtained is purified by recrystallization or the like, if necessary.
なお一般式（Ｉｆ）において、Ｒがアシル基の場合は、
反応に使用するアルカリ剤や反応温度等にょ夛、二量化
反応とともに脱アシル化反応も起る場合がある。特ＫＲ
がアセチル基の場合は通常脱アセチル化反応を併発して
、反応終了混合物中の一般式（１）で表わされる化合物
はジヒドロキシ体（ｌとして得られる。従って一般式（
１）で表わされる化合物の用途目的によりては、アシル
基の加水分解も同時に起ることは却って有利である。In addition, in general formula (If), when R is an acyl group,
Depending on the alkaline agent used in the reaction, the reaction temperature, etc., a deacylation reaction may occur along with the dimerization reaction. Special KR
When is an acetyl group, a deacetylation reaction is usually carried out, and the compound represented by the general formula (1) in the reaction mixture is obtained as a dihydroxy compound (I).
Depending on the intended use of the compound represented by 1), it may be advantageous for the acyl group to be hydrolyzed at the same time.
次に本発明の実施例について説明する。 Next, examples of the present invention will be described.
実施例１
１１容ＳＵＳ製加圧反応機に、４−ヒドロキシ−４′−
ブロムビフェニル６０．０ＩＩ（０，２４モル）、メタ
ノール１００＃、１０俤（重量、以下同じ）水酸化ナト
リウム水溶液３００１１及び５チパ２ジウムーカーメン
触媒１３＃ｔ−仕込み、攪拌下１２０℃、４〜５気圧／
ｉの加圧下で４時間反応させた。Example 1 4-Hydroxy-4'-
Brombiphenyl 60.0 II (0.24 mol), methanol 100 #, 10 k (weight, the same hereinafter) sodium hydroxide aqueous solution 30011 and 5 chips didium-carmene catalyst 13 #t-prepared, stirred at 120°C, 4~ 5 atm/
The reaction was carried out for 4 hours under pressure of i.
反応混合物を室温に冷却後、固形物（４，４Ｉｎ−ジヒ
ドロキシクォーターフェニルのジナトリウム塩と触媒と
の混合物）をｒ取し、該固形物を１．５１反応フラスコ
に仕込み、 Ｎ、Ｎ−ジメチルホルムアミド１ｌｔ−加
えて攪拌下で加熱し、１時間後熱濾過した。Ｐ液は冷却
後希硫酸で酸析し、析出物を濾過し、メタノール洗浄し
乾燥して、白色結晶性粉末の４，４＃−ジヒドロキシク
ォーターフェニル２４．５１ｉｔ−得た。収率６０．１
’１゜融点４２０℃。（高速液体クロマトグラフ分析
による）純度９８．５％。After cooling the reaction mixture to room temperature, a solid substance (a mixture of disodium salt of 4,4In-dihydroxyquaterphenyl and a catalyst) was collected, and the solid substance was charged into a 1.51 reaction flask, and N,N-dimethyl 1 lt of formamide was added, heated under stirring, and after 1 hour filtered hot. After cooling, the P solution was precipitated with dilute sulfuric acid, and the precipitate was filtered, washed with methanol, and dried to obtain 24.51 it of 4,4#-dihydroxyquaterphenyl as a white crystalline powder. Yield 60.1
'1° Melting point 420°C. Purity 98.5% (by high performance liquid chromatography analysis).
このもののＮ、Ｎ−ジメチルホルムアミドによる再結晶
精製品の融点４４０℃、純度９９．９優。A purified product of this product recrystallized with N,N-dimethylformamide has a melting point of 440°C and a purity of 99.9.
反応混合物の濾過母液からは酸析により４−ヒドロキシ
ビフェニルと４−ヒドロキシ−４′−ブロムビフェニル
の混合物（前者６６俤、後者３４％）８．４！Ｉが、又
Ｎ、Ｎ−ジメチルホルムアミド溶液の酸析母液からは、
４．４”−ジヒドロキシクォーターフェニル５．２＃（
純度９８．４ ％ ）が回収され九。From the filtered mother liquor of the reaction mixture, a mixture of 4-hydroxybiphenyl and 4-hydroxy-4'-brombiphenyl (66 g of the former, 34% of the latter) was obtained by acid precipitation, 8.4! I is also obtained from the acid precipitation mother liquor of N,N-dimethylformamide solution,
4.4”-dihydroxyquaterphenyl 5.2#(
A purity of 98.4%) was recovered.
合計収量２９．７ ＃ 、合計収率７３．２チ。パラジ
ウム−カーダン触媒の回収量は１２．５＃（回収率９６
．１％、はとんどハンドリングによるロス）であった。Total yield 29.7 #, total yield 73.2 #. The recovery amount of palladium-cardan catalyst was 12.5# (recovery rate 96
．． 1% was mostly loss due to handling).
実施例２
実施例１と同様に操作し、５％・昔ラジウムーカ−Ｍン
触媒は前回反応回収分に不足量を追加して反覆使用し、
５回反応を行なった。その結果を第１表に示す。Example 2 The same procedure as in Example 1 was carried out, and the 5% old radium carbon catalyst was used repeatedly by adding the insufficient amount to the amount recovered from the previous reaction.
Reactions were performed five times. The results are shown in Table 1.
第 １
表
反覆 収量 収率 純 度回ｍ
回数 （１次＋２次）ｅｓ 係 注１）
２９．７
３０．０
２９．５
２８．３
２８．０
２７．５
７３．２
７４．０
７２．７
６９．８
６９．０
６７．８
９８．５〜９８．４
９９．７〜９８．０
９９．１〜９８．２
９７．４〜９９６２
９９．０〜９８゜９
９９．６〜９８．５
８．４
８．４
８．３
８．９
９．０
９．３
注１）４−ヒドロキシビフェニルと４−ヒドロキシ−４
′−ブロムビフェニルの混合物
２） 実施例１
実施例３
実施例２で５回反覆して回収した５慢ノやラックムーカ
ーメン触媒を水洗しく７０℃で乾燥した後、常法によシ
窒素気流下３００℃まで３時間で昇温したのち水素気流
に切り換え、３６０℃に３時間保ち、再生を行なりた。Table 1 Repetition Yield Yield Purity times m Number of times (1st + 2nd) es Note 1)
29.7 30.0 29.5 28.3 28.0 27.5 73.2 74.0 72.7 69.8 69.0 67.8 98.5~98.4 99.7~98.0 99.1-98.2 97.4-9962 99.0-98°9 99.6-98.5 8.4 8.4 8.3 8.9 9.0 9.3 Note 1) 4-Hydroxy Biphenyl and 4-hydroxy-4
Mixture of '-brombiphenyl 2) Example 1 Example 3 The 5-brom biphenyl catalyst recovered by repeating the process 5 times in Example 2 was washed with water and dried at 70°C, and then washed with a nitrogen stream in a conventional manner. After raising the temperature to below 300°C over 3 hours, the hydrogen flow was switched to, and the temperature was kept at 360°C for 3 hours to perform regeneration.
得られた再生触媒１２．ＯＩに新触媒１．０ ！Ｉｔ追
加して、実施例１と同様にして反応を行なった。合計収
量３０．８１１．収率７５．９％。（純度９９．１〜９
９．８ｃＩｂ、）回収４−ヒドロキシピフェニルと４−
ヒドロキシ−４′−ブロムビフェニルの量８．３＆。Obtained regenerated catalyst 12. New catalyst 1.0 for OI! The reaction was carried out in the same manner as in Example 1 with the addition of It. Total yield 30.811. Yield 75.9%. (Purity 99.1-9
9.8cIb,) recovered 4-hydroxypiphenyl and 4-
Amount of hydroxy-4'-brombiphenyl 8.3&.
実施例４
４−アセトキシ−４−ブロムＣフェニル６０．０ＩＣ０
，２０６モル）、メタノール１００ＩＩ、１０チ水酸化
ナトリウム水溶液３００ｊ’及び５俤ノ９ラジウム−カ
ーメン触媒１３１′ｔ−用いて実施例１と同様に操作し
、 ４．４”−ジヒドロキシクォーターフェニルを得た
。合計収量２７．５Ｊ’、収率７９． Ｏｔ４゜純度９
８．５〜９９．Ｏ１融点４１５℃〜４２０℃。Example 4 4-acetoxy-4-bromoC phenyl 60.0 IC0
, 206 mol), methanol 100II, 10% sodium hydroxide aqueous solution 300j', and 5 9 radium-carmene catalyst 131't- to obtain 4.4''-dihydroxyquaterphenyl. Total yield 27.5J', yield 79.Ot4゜purity 9
8.5-99. O1 melting point 415°C to 420°C.
実施例５
１Ｉ容反応ＷＡに、４−ヒドロキシ−４′−ブロムビフ
ェニル６０．０ｊ、エチレングリコール１５０＃、１０
％水酸化ナトリウム水溶液３００Ｉｉ及び５チノ４ラジ
ウム−カーメン触媒７．５１を仕込み、攪拌下（常圧で
）反応混合物の還流温度（約１０５℃）で５時間反応さ
せた。反応混合物を室温に冷却し、２５％希硫酸でｐＨ
３としたのち固形物をＰ別した。固形物にＮ、Ｎ−ジメ
チルホルムアミド１０００ａ＋７を加えて加熱し、約１
２０℃で熱濾過した。ｒ液ｆ：１５℃に冷却して晶析物
を濾過、洗浄、乾燥して、白色結晶性粉末の４，４Ｍ−
ジヒドロキシクォーターフェニル２４．５１９を得た。Example 5 To 1 I volume reaction WA, 60.0j of 4-hydroxy-4'-brombiphenyl, 150# of ethylene glycol, 10
300 Ii of aqueous sodium hydroxide solution and 7.5 l of a 5-tino-4-radium-carmene catalyst were charged, and the reaction mixture was reacted for 5 hours at the reflux temperature (about 105° C.) of the reaction mixture under stirring (at normal pressure). The reaction mixture was cooled to room temperature and adjusted to pH with 25% dilute sulfuric acid.
3, and then the solid matter was separated into P. Add N,N-dimethylformamide 1000a+7 to the solid and heat it to about 1
Hot filtration was performed at 20°C. R liquid f: Cool to 15°C, filter, wash, and dry the crystallized product to obtain 4,4M-white crystalline powder.
Dihydroxyquaterphenyl 24.519 was obtained.
純度９９、１１゜融点４２０℃。酸析母液からの回収４
．４が一ジヒドロキシクォーターフェニル４．８１６純
度９９．０係。融点４２０℃。合計収量２９．３Ｉｉ。Purity 99, 11°, melting point 420°C. Recovery from acid precipitation mother liquor 4
．． 4 is mono-dihydroxyquaterphenyl 4.816 purity 99.0 ratio. Melting point: 420°C. Total yield 29.3Ii.
合計状＄７２．１１
実施例６
実施例１で、４−ヒドロキシ−４′−ブロムビフェニル
６０．ＣＭ＋の代シに、４−メトキシ−４′−ブロムビ
フェニル６３．０１９（０，２４モル）ｔ−使用シた以
外は同様に加圧反応して、得られた反応混合物を１５℃
に冷却、濾過した。ｒ取固形物にＮ、Ｎ’−ジメチルホ
ルムアミド１１を加えて加熱、熱濾過して触媒を分離し
たのち、ｒ液を１５℃に冷却、濾過、乾燥して白色結晶
状の４，４Ｍ−ジメトキシクォーターフェニル２４．５
Ｆｔ−得た。収率５５．８俤。Total $72.11 Example 6 In Example 1, 4-hydroxy-4'-brombiphenyl 60. A pressure reaction was carried out in the same manner, except that 63.019 (0.24 mol) of 4-methoxy-4'-brombiphenyl was used in place of CM+, and the resulting reaction mixture was heated at 15°C.
Cooled and filtered. After adding N,N'-dimethylformamide 11 to the r-removed solid, heating and hot filtration to separate the catalyst, the r-liquid was cooled to 15°C, filtered, and dried to obtain white crystalline 4,4M-dimethoxy. Quarter phenyl 24.5
Ft-obtained. Yield: 55.8 yen.
融点３３６℃。純度９８．’５係。Melting point: 336°C. Purity 98. '5 section.
実施例７
実施例５と同様の装置を用いて、４−ヒドロキシ−４′
−ブロムビフェニルの代シに４−アセトキシ−４’−／
ロルビフェニル６０．０ｇ、エチレングリコール１５０
ｊ’、１０％水酸化ナトリウム水溶液３００Ｉ及び５係
ノぐラジウム−カーボン触媒１２．４１を仕込み、攪拌
下常圧で還流温度（約１０５℃）で５時間反応させた。Example 7 Using the same equipment as in Example 5, 4-hydroxy-4'
-4-acetoxy-4'-/ in place of brombiphenyl
60.0g of lorbiphenyl, 150g of ethylene glycol
300 I of a 10% aqueous sodium hydroxide solution and 12.4 l of a radium-carbon catalyst were charged, and the mixture was reacted with stirring at normal pressure at a reflux temperature (approximately 105° C.) for 5 hours.
反応後実施例５と同様に操作して白色結晶性粉末の４，
４Ｉ−ジヒドロキシクォーターフェニル２０．８Ｎを得
た。収率５０．９係。After the reaction, a white crystalline powder of 4,
20.8N of 4I-dihydroxyquaterphenyl was obtained. Yield: 50.9.
純度９９．７１融点４２０℃＊ ｆ九ＮｔＮ−ｐメチル
ホルムアミド溶液の酸析母液から４，４＃−ジヒドロキ
シ−クォーターフェニル４．８Ｊｌ（純度９８．８１）
が回収された。合計収量２５．６．９；合計収率６２．
６５ｋ。Purity: 99.71 Melting point: 420°C
was recovered. Total yield 25.6.9; Total yield 62.
65k.
本発明によれば、金属粉や特殊な装置、操作を必要とせ
ず、安全、衛生及び公害防止上からも何ら問題を生ずる
恐れなく、一般式（１）で表わされる高品質の化合物を
高収率で製造することができる。According to the present invention, the high-quality compound represented by the general formula (1) can be produced in high yield without requiring metal powder, special equipment, or operation, and without causing any problems in terms of safety, hygiene, and pollution prevention. can be manufactured at a high rate.
Claims (2)
ル基を、Ｘはハロゲン原子をそれぞれ示す。〕で表わさ
れる４−ヒドロキシ−４′−ハロゲノビフェニル又はそ
の誘導体を、不活性有機極性溶媒中で、アルカリ金属又
はアルカリ土類金属の水酸化物、炭酸塩或いは重炭酸塩
の１種又は２種以上の共存下に、パラジウムを触媒とし
脱ハロゲン化二量化することを特徴とする、一般式（
I ） ▲数式、化学式、表等があります▼（ I ） 〔一般式（ I ）で、Ｒは一般式（II）における定義に
同じ。〕 で表わされる４，４′″−ジヒドロキシクォーターフェ
ニル又はその誘導体の製造方法。(1) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In general formula (II), R represents a hydrogen atom, an alkyl group, or an acyl group, and X represents a halogen atom. ] 4-Hydroxy-4'-halogenobiphenyl or a derivative thereof is mixed with one or two of alkali metal or alkaline earth metal hydroxides, carbonates, or bicarbonates in an inert organic polar solvent. In the coexistence of the above, the general formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In general formula (I), R is the same as the definition in general formula (II). ] A method for producing 4,4'''-dihydroxyquaterphenyl or a derivative thereof.
範囲第１項記載の４，４′″−ジヒドロキシクォーター
フェニル又はその誘導体の製造方法。(2) A method for producing 4,4'''-dihydroxyquaterphenyl or a derivative thereof according to claim 1, which comprises dehalogenating and dimerizing in the presence of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1075173A JP2716512B2 (en) | 1989-03-29 | 1989-03-29 | Process for producing 4,4 '""-dihydroxyquarterphenyl or a derivative thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1075173A JP2716512B2 (en) | 1989-03-29 | 1989-03-29 | Process for producing 4,4 '""-dihydroxyquarterphenyl or a derivative thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02255634A true JPH02255634A (en) | 1990-10-16 |
| JP2716512B2 JP2716512B2 (en) | 1998-02-18 |
Family
ID=13568545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1075173A Expired - Fee Related JP2716512B2 (en) | 1989-03-29 | 1989-03-29 | Process for producing 4,4 '""-dihydroxyquarterphenyl or a derivative thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2716512B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665153A (en) * | 1992-04-28 | 1994-03-08 | Ihara Chem Ind Co Ltd | Production of asymmetric biaryl derivative |
| US5319149A (en) * | 1992-12-11 | 1994-06-07 | General Electric Company | Bis[4'-(4-hydroxyphenyl)-phenyl]alkanes and polycarbonates prepared therefrom |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5653631A (en) * | 1979-10-08 | 1981-05-13 | Sumitomo Chem Co Ltd | Preparation of diphenol |
| JPS61293932A (en) * | 1985-06-14 | 1986-12-24 | インペリアル ケミカル インダストリ−ズパブリツク リミテイド カンパニ− | Aromatic compound and manufacture |
| JPS62212328A (en) * | 1986-03-12 | 1987-09-18 | Hitachi Chem Co Ltd | Production of biphenyl compound |
-
1989
- 1989-03-29 JP JP1075173A patent/JP2716512B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5653631A (en) * | 1979-10-08 | 1981-05-13 | Sumitomo Chem Co Ltd | Preparation of diphenol |
| JPS61293932A (en) * | 1985-06-14 | 1986-12-24 | インペリアル ケミカル インダストリ−ズパブリツク リミテイド カンパニ− | Aromatic compound and manufacture |
| JPS62212328A (en) * | 1986-03-12 | 1987-09-18 | Hitachi Chem Co Ltd | Production of biphenyl compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665153A (en) * | 1992-04-28 | 1994-03-08 | Ihara Chem Ind Co Ltd | Production of asymmetric biaryl derivative |
| US5319149A (en) * | 1992-12-11 | 1994-06-07 | General Electric Company | Bis[4'-(4-hydroxyphenyl)-phenyl]alkanes and polycarbonates prepared therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2716512B2 (en) | 1998-02-18 |
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