JPH03109342A - Production of 4,4'-dihydroxydiphenylmethane - Google Patents
Production of 4,4'-dihydroxydiphenylmethaneInfo
- Publication number
- JPH03109342A JPH03109342A JP24673089A JP24673089A JPH03109342A JP H03109342 A JPH03109342 A JP H03109342A JP 24673089 A JP24673089 A JP 24673089A JP 24673089 A JP24673089 A JP 24673089A JP H03109342 A JPH03109342 A JP H03109342A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- dihydroxydiphenylmethane
- reaction
- alcohol
- acid
- 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
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 15
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 7
- PVAONLSZTBKFKM-UHFFFAOYSA-N diphenylmethanediol Chemical compound C=1C=CC=CC=1C(O)(O)C1=CC=CC=C1 PVAONLSZTBKFKM-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 abstract description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- -1 phenol Chemical compound 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000010926 purge Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 4
- 241000220317 Rosa Species 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002633 crown compound Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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
- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 description 1
- ZBSGNEYIENETRW-UHFFFAOYSA-N 2,3-bis(hydroxymethyl)phenol Chemical compound OCC1=CC=CC(O)=C1CO ZBSGNEYIENETRW-UHFFFAOYSA-N 0.000 description 1
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical group CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000007031 hydroxymethylation reaction Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- 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]
本発明はフェノールとホルムアルデヒドとからジヒドロ
キシジフェニルメタンを製造する方法に関し、特に4.
4−ジヒドロキシジフェニルメタンを選択的に製造する
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing dihydroxydiphenylmethane from phenol and formaldehyde, particularly in 4.
The present invention relates to a method for selectively producing 4-dihydroxydiphenylmethane.
フェノールとホルムアルデヒドを酸性条件下反応させて
得られるジヒドロキシジフェニルメタンは通常2.2°
一体、 2.4’一体、 4.4’−体の3つの異
性体の混合物となる。Dihydroxydiphenylmethane obtained by reacting phenol and formaldehyde under acidic conditions is usually 2.2°
It is a mixture of three isomers: monolithic, 2.4′-isomer, and 4.4′-isomer.
この3つの異性体の混合物であるジヒドロキシジフェニ
ルメタンは、エポキシ樹脂の原料等、高分子の原料モノ
マーとして有用な化合物である。Dihydroxydiphenylmethane, which is a mixture of these three isomers, is a compound useful as a raw material monomer for polymers such as a raw material for epoxy resins.
また、4.4−ジヒドロキシジフェニルメタンは、従来
のジヒドロキシジフェニルメタン混合体に比べてその高
分子体は耐熱性等の面で改善されることが知られており
、非常に興味深い化合物である。Furthermore, 4,4-dihydroxydiphenylmethane is a very interesting compound as it is known that its polymer is improved in terms of heat resistance and the like compared to conventional dihydroxydiphenylmethane mixtures.
〔従来の技術l
従来、ジヒドロキシジフェニルメタンは工業的には、ホ
ルムアルデヒドとアルデヒドに対し過剰13〜30モル
倍)のフェノールを無溶媒でl々の酸を共存させ加熱撹
拌することにより製造されていた(例えば特開昭55−
124730号明細書等)、この様にして得られるジヒ
ドロキシジフェニルメタンの異性体比は1通常2.2一
体が15〜25%、2.4゜体が40〜45%、 4
.4’一体が30〜40%となる64.4°−ジオキシ
ジフェニルメタンの選択的合成例もいくつか提案されて
いる0例えば、特公昭49−6310号明細書には、酸
性条件下アルキル置換尿素を添加物として共存させて反
応を行うと4.4’−体が68〜74%の選択率で得ら
れ、このときモノメチル尿素を添加物として用いる場合
が最も4.4’−体選択率が良く、74%となることが
記載されている。また、特公昭48−38694号明細
書によれば、極性非プロトン性溶媒存在下に酸触媒を用
いてフェノール及びホルマリンを加熱撹拌すると52〜
82%の選択率で4.4一体が得られる。[Prior art l] Conventionally, dihydroxydiphenylmethane has been industrially produced by coexisting formaldehyde and phenol (13 to 30 molar excess relative to aldehyde) in the presence of various acids without a solvent and heating and stirring the mixture ( For example, JP-A-55-
124730, etc.), the isomer ratio of dihydroxydiphenylmethane obtained in this way is 1, usually 15-25% of 2.2-unit, 40-45% of 2.4-unit, 4
.. Some examples of selective synthesis of 64.4°-dioxydiphenylmethane with 30 to 40% of 4' monomers have been proposed. When the reaction is carried out in the presence of monomethylurea as an additive, the 4.4'-isomer is obtained with a selectivity of 68 to 74%, and when monomethylurea is used as an additive, the 4.4'-isomer selectivity is the highest. It is stated that the ratio is 74% at best. According to Japanese Patent Publication No. 48-38694, when phenol and formalin are heated and stirred using an acid catalyst in the presence of a polar aprotic solvent, the
4.4 integrals are obtained with a selectivity of 82%.
しかしながら、アルキル置換尿素を添加する系において
は5選択率は74%止りであり、なおかつ尿素のメチロ
ール化物が副生ずる。また、極性非プロトン性溶媒下で
行う系においては、高選択率の得られる溶媒はジエチル
ホルムアミド(沸点176〜177℃、選択率77%)
、ジメチルホルムアミド(沸点152℃、選択率82%
)等の高沸点溶媒であり、かつ、溶媒として高価であり
、いずれも工業的製法としては実用的でない。However, in a system in which alkyl-substituted urea is added, the 5 selectivity is only 74%, and methylolated urea is produced as a by-product. In addition, in systems run under polar aprotic solvents, the solvent that provides high selectivity is diethylformamide (boiling point 176-177°C, selectivity 77%).
, dimethylformamide (boiling point 152°C, selectivity 82%
), etc., and are expensive as solvents, and both are impractical for industrial production methods.
〔発明が解決しようとする課題1
本発明の目的は、このような状況のもとて高分子の原料
モノマーとして興味深い4.4゛−ジヒドロキシジフェ
ニルメタンを選択的に製造する新規な方法を提供するこ
とにある。[Problem to be Solved by the Invention 1] The purpose of the present invention is to provide a new method for selectively producing 4,4'-dihydroxydiphenylmethane, which is interesting as a raw material monomer for polymers under these circumstances. It is in.
〔課題を解決するための手段1
本発明はジヒドロキシジフェニルメタンを製造するに際
して、先ず塩基性条件下で4.4°−ジヒドロキシジフ
ェニルメタンの中間体であるパラヒドロキシベンジルア
ルコールを選択的に合成し1次いで反応系を酸を用い酸
性にし、必要に応じフェノールを加え加熱撹拌すること
により高選択的に4.4°−ジヒドロキシジフェニルメ
タンを合成することに成功した。[Means for Solving the Problems 1] When producing dihydroxydiphenylmethane, the present invention first selectively synthesizes parahydroxybenzyl alcohol, which is an intermediate of 4.4°-dihydroxydiphenylmethane, under basic conditions, and then reacts it. By making the system acidic using an acid, adding phenol as necessary and heating and stirring, we succeeded in synthesizing 4.4°-dihydroxydiphenylmethane with high selectivity.
すなわち1本発明は、フェノールとホルムアルデヒド源
とからジヒドロキシジフェニルメタンを製造する方法に
おいて、フェノールとホルムアルデヒド源とを、アルコ
ール系有機溶媒中、塩基性条件下で、クラウンエーテル
を加えて反応させてパラヒドロキシベンジルアルコール
を生成させ、次いで反応液を酸性化し、更にフェノール
を反応させることを特徴とする4、4−ジヒドロキシジ
フェニルメタンの製造方法である。That is, the present invention provides a method for producing dihydroxydiphenylmethane from phenol and a formaldehyde source, in which phenol and a formaldehyde source are reacted in an alcoholic organic solvent under basic conditions with the addition of crown ether to produce parahydroxybenzyl. This is a method for producing 4,4-dihydroxydiphenylmethane, which is characterized by producing alcohol, then acidifying the reaction solution, and further reacting with phenol.
凰」
本発明においてフェノールと反応させるホルムアルデヒ
ド源としては、ホルマリン、バラホルムアルデヒド、低
級アルコールのへミホルマール。In the present invention, formaldehyde sources to be reacted with phenol include formalin, paraformaldehyde, and lower alcohol hemiformal.
炭素数2〜5の多価アルコールのへミホルマールが上げ
られるが、中でもバラホルムアルデヒドが好適である。Examples include hemiformal, which is a polyhydric alcohol having 2 to 5 carbon atoms, and among them, paraformaldehyde is preferred.
ホルマリンは少量用いる分には構わないが、反応系内の
含水層が増加すると、それにに伴いバラ選択性が若干低
下する。Formalin may be used in small amounts, but as the water-containing layer in the reaction system increases, the rose selectivity decreases slightly.
特にバラホルムアルデヒドより昇華精製したホルムアル
デヒドを用いると、反応は速やかに進行し副反応も押え
られ、高収率で反応をを行なうことができる。In particular, when formaldehyde purified by sublimation from formaldehyde is used, the reaction proceeds quickly, side reactions are suppressed, and the reaction can be carried out in high yield.
■
塩基性条件を作る塩基としては、水酸化ナトリウム、水
酸化カリウム等の金属水酸化物、ナトリウムメトキシド
、ナトリウムエトキシド、 tert−ブトキシカリウ
ム等の金属アルコキシド、水酸化ナトリウム等の金属水
酸化物などフェノールよりも塩基性度の高い含金属塩基
が用いられる。■ Bases that create basic conditions include metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide, and metal hydroxides such as sodium hydroxide. A metal-containing base with higher basicity than phenol, such as phenol, is used.
アルコール7、−2と
本発明の方法において用いられるアルコール系有機溶媒
としては、メタノール、エタノール、 n−プロパツー
ル、i−プロパツール、n−ブタノール。Examples of alcohol-based organic solvents used in alcohol 7, -2 and the method of the present invention include methanol, ethanol, n-propanol, i-propanol, and n-butanol.
i−ブタノール及びこれら以上の炭素数を有する炭素数
lO以下のアルキルアルコール、エチレングリコール、
2.3−ブタンジオール等の多価アルコール、ベンジル
アルコールやそれに類する芳香族を含むアルコール等種
々のアルコールが単独又は混合して用いられる。これら
のうち特にエタノール、n−プロパツール、i−プロパ
ツール、i−ブタノール等の低級アルコールは、選択率
が高く、かつ、反応速度も早いので好ましい。i-butanol and alkyl alcohols having a carbon number of 10 or less, ethylene glycol,
Various alcohols such as polyhydric alcohols such as 2.3-butanediol, benzyl alcohol, and similar aromatic alcohols may be used alone or in combination. Among these, lower alcohols such as ethanol, n-propanol, i-propanol, and i-butanol are particularly preferred because of their high selectivity and fast reaction rate.
本発明のアルコール系有機溶媒としては、これらのアル
コールに非アルコール系有機溶媒を混合して用いること
ができる。混合できる非アルコール溶媒としては、ベン
ゼン、トルエン、キシレンをはじめとする芳香族系溶媒
、ペンタン°、ヘキサン、ヘプタンをはじめとする脂肪
族系溶媒、クロロホルム、ジクロロメタン、ジクロロエ
タン等のハロゲン化アルキル、ジメチルアセトアミド、
ジメチルホルムアミド等のアミド類、ジメチルスルホキ
シド等のスルホキシド類、アセトニトリル、ベンゾニト
リル等のニトリル類等の種々の有機溶媒が挙げられる。As the alcoholic organic solvent of the present invention, a non-alcoholic organic solvent can be mixed with these alcohols. Non-alcoholic solvents that can be mixed include aromatic solvents such as benzene, toluene, and xylene, aliphatic solvents such as pentane, hexane, and heptane, alkyl halides such as chloroform, dichloromethane, and dichloroethane, and dimethylacetamide. ,
Various organic solvents include amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, and nitriles such as acetonitrile and benzonitrile.
非アルコール温媒の混合率は70%以下が好ましく、7
0%より多く用いると、反応速度が遅くなる。一般には
アルコールのみからなる単独又は混合系溶媒を用いるこ
とが好ましい。The mixing ratio of the non-alcoholic heating medium is preferably 70% or less, and 7
If more than 0% is used, the reaction rate will be slow. Generally, it is preferable to use a solvent consisting of alcohol alone or in combination.
クラウンエーテル
本発明の方法において、添加物として加えるクラウンエ
ーテル類としては1例えば1B−クラウンエーテル−6
、ジベンゾ−18−クラウンエーテル−6、ジシクロへ
キサノー18−クラウンエーテル−6、ベンゾ−18−
クラウンエーテル−6、シクロへキサノー18−クラウ
ンエーテル−6等のいわゆる18−クラウンエーテル−
6類、また上記に相当する!5−クラウンエーテルー5
類、 24−クラウンエーテル−8類等の種々の環の大
きさのクラウンエーテル類、及びビナフトールや芳香族
を環内に有する稲々のクラウンエーテル類などが挙げら
れる。また、上記のクラウンエーテル類を含む高分子も
本発明でいうクラウンエーテル類に含まれる。Crown ether In the method of the present invention, examples of crown ethers added as additives include 1, for example, 1B-crown ether-6.
, dibenzo-18-crown ether-6, dicyclohexano-18-crown ether-6, benzo-18-
So-called 18-crown ethers such as crown ether-6 and cyclohexanor 18-crown ether-6
Category 6, also equivalent to the above! 5-Crown Aether 5
Examples include crown ethers with various ring sizes such as 24-crown ether-8, and rice crown ethers having binaphthol or an aromatic group in the ring. Moreover, polymers containing the above-mentioned crown ethers are also included in the crown ethers referred to in the present invention.
クラウンエーテルの固定化方法として各種のものが公知
(例えば、平岡道夫「クラウン化合物」参照)である、
−殻内なものとしてジベンゾ−18−クラウン−6とア
ルデヒドとの付加重合型高分子クラウンエーテル、ジア
ミノベンゾ−18−クラウン−6とジ酸クロリド、ジイ
ソシアネート等との重縮金型クラウンエーテルポリマー
、ポリビニルクラウン化合物等のポリマーが合成されて
いる。Various methods are known for immobilizing crown ethers (for example, see Michio Hiraoka's "Crown Compounds").
- Addition-polymerized polymeric crown ether of dibenzo-18-crown-6 and aldehyde, polycondensation-type crown ether polymer of diaminobenzo-18-crown-6 and diacid chloride, diisocyanate, etc., as inside the shell; Polymers such as polyvinyl crown compounds have been synthesized.
醒
反応に用いる酸は、塩酸、硫酸、リン酸、&A酸、過塩
素酸、パラトルエンスルホン酸、スルホン基型イオン交
換樹脂、酸性白土、シリカアルミナ等、各種の酸性触媒
を使用することができる。Various acidic catalysts can be used as the acid used in the oxidation reaction, such as hydrochloric acid, sulfuric acid, phosphoric acid, &A acid, perchloric acid, para-toluenesulfonic acid, sulfone group type ion exchange resin, acid clay, silica alumina, etc. .
反12に件
(第一段反応)
反応は1通常窒素雰囲気下で、上記のアルコール系有機
溶媒から成る単独あるいは混合溶媒lβに対し、フェノ
ールを0.1−10モル、好ましくは0.3〜3モル、
ホルムアルデヒド類をフェノールに対し、0.旧〜5当
量、好ましくは0.1−1当量、塩基をフェノールに対
し0.1−10当量、好ましくは0.3〜1.2当量及
びクラウンエーテルを塩基に対し0.1−10当量、好
ましくは0.8〜5当量を加えて、先ずフェノールのヒ
ドロキシメチル化を行う。Reaction 12 (first stage reaction) The reaction is carried out by adding 0.1 to 10 moles of phenol, preferably 0.3 to 10 moles of phenol, to lβ, a single or mixed solvent consisting of the above-mentioned alcohol-based organic solvents, usually under a nitrogen atmosphere. 3 moles,
Formaldehyde to phenol, 0. 5 equivalents, preferably 0.1-1 equivalents of base, 0.1-10 equivalents, preferably 0.3-1.2 equivalents of base to phenol, and 0.1-10 equivalents of crown ether to base, Preferably, 0.8 to 5 equivalents are added to hydroxymethylate the phenol first.
反応温度は0〜130℃、好ましくは30〜80℃の範
囲である1反応時間は反応温度及び用いた溶媒によって
左右され、例えば反応温度が60℃のときには反応時間
は通常6〜24時間となる6本ヒドロキシメチル化反応
は低温の方がバラ選択性は高いが、それに伴い反応速度
が低下する。The reaction temperature is in the range of 0 to 130°C, preferably 30 to 80°C. The reaction time depends on the reaction temperature and the solvent used, for example, when the reaction temperature is 60°C, the reaction time is usually 6 to 24 hours. Although the 6-hydroxymethylation reaction has higher rose selectivity at lower temperatures, the reaction rate decreases accordingly.
反応はホルムアルデヒド類がなくたったところで終了し
、反応系を室温に戻す。The reaction ends when formaldehyde is no longer present, and the reaction system is returned to room temperature.
(第二段反応ン
次いで室温にもどった反応系に上記の酸を加え1反応系
内の塩基を中和し、更に過剰の酸、好ましくは0.3〜
20モル%の酸が存在する様に調整する。また、フェノ
ールが反応系内のヒドロキシメチルフェノールに対し3
〜50倍、好ましくは6〜25倍となるように、必要に
応じフェノールを添加する。(Second stage reaction) Next, add the above acid to the reaction system which has returned to room temperature to neutralize the base in the reaction system, and add excess acid, preferably 0.3~
Adjust so that 20 mol% acid is present. In addition, phenol is 3
Phenol is added as necessary to increase the amount by 50 times, preferably 6 to 25 times.
このように調整した第一段反応生成物を室温〜J20℃
、好ましくは60〜90℃で窒素雰囲気下に加熱撹拌す
ることによって、4.4°−ジヒドロキシジフェニルメ
タンが得られる。第二段反応に要する時間は1〜10時
間である。The first stage reaction product prepared in this way was heated to room temperature to J20°C.
4.4°-dihydroxydiphenylmethane is obtained by heating and stirring, preferably at 60 to 90° C. under a nitrogen atmosphere. The time required for the second stage reaction is 1 to 10 hours.
反応終了後反応液を室温に戻し、水洗した後、有機層を
分離し1次いで蒸留などの方法により未反応フェノール
及び溶媒を除去し、 4.4’−ジヒドロキシジフェ
ニルメタンを得る。更に純度を高める必要がある場合は
、トルエン、エチルベンゼン、キシレン等の芳香族炭化
水素類を用いて再結晶する。After the reaction is completed, the reaction solution is returned to room temperature, washed with water, the organic layer is separated, and unreacted phenol and solvent are removed by distillation or other methods to obtain 4,4'-dihydroxydiphenylmethane. If it is necessary to further increase the purity, recrystallization is performed using aromatic hydrocarbons such as toluene, ethylbenzene, and xylene.
以下、実施例に基いて本発明の詳細な説明するが1本発
明はこれらの実施例によって限定されず、種々の実施態
様があり得る。Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples, and may have various embodiments.
実施例1
15n+1の密閉式耐圧ガラス反応器に、イソプロピル
アルコール5ml、フェノール0.544g (5,7
8ミリモル)、水酸化ナトリウム0.242g+5.7
8ミリモル)及びI8−クラウン−6−エーテル1.5
33g (5,78ミリモル)を入れ、窒素で置換した
後に80℃に加熱して攪拌し、内容物が溶けたのを確認
して温度を室温にまでもどした。Example 1 5 ml of isopropyl alcohol and 0.544 g of phenol (5,7
8 mmol), sodium hydroxide 0.242g + 5.7
8 mmol) and 1.5 I8-crown-6-ether
After adding 33 g (5.78 mmol) and purging with nitrogen, the mixture was heated to 80° C. and stirred. After confirming that the contents had melted, the temperature was returned to room temperature.
昇華精製したバラホルムアルデヒドをイソプロピルアル
コールに溶かした濃度が0.67モル/I2の純粋へミ
ホルマール・イソプロピルアルコール溶液0.86ta
l (ホルムアルデヒド0.578ミリモル)を加え、
再び窒素で置換し、50℃で24時間加熱撹拌し、第一
段目の反応生成物を得た。A pure hemiformal isopropyl alcohol solution with a concentration of 0.67 mol/I2 in which sublimated rose formaldehyde is dissolved in isopropyl alcohol. 0.86 ta
l (0.578 mmol formaldehyde) was added,
The atmosphere was again purged with nitrogen, and the mixture was heated and stirred at 50° C. for 24 hours to obtain a first-stage reaction product.
反応液中の生成物を液体クロマトグラフィーで分析した
結果は、バラヒドキシベンジルアルコールとオルトヒド
ロキシベンジルアルコールの2種類で、バラヒドキシベ
ンジルアルコールの選択率は88.3%であり、ホルム
アルデヒドの転化率は100%、ホルムアルデヒドを基
にした収率は85.6%であった。Analysis of the products in the reaction solution by liquid chromatography revealed that there were two types of products: barahydroxybenzyl alcohol and orthohydroxybenzyl alcohol, and the selectivity of barahydroxybenzyl alcohol was 88.3%, indicating that formaldehyde conversion The yield was 100% and the yield based on formaldehyde was 85.6%.
この反応混液に12N−1icjを加え、0.05ミリ
モルの酸が過剰となる様に調整した。この酸性液を窒素
置換した後、80℃に加温し、4時間撹拌した。12N-1icj was added to this reaction mixture to adjust the amount of acid to be 0.05 mmol in excess. After purging this acidic liquid with nitrogen, it was heated to 80°C and stirred for 4 hours.
反応混液を室温までもどし、分析したところ反応液中に
はヒドロキシベンジルアルコールは認められず、生成物
は4.4−ジヒドロキシジフェニルメタン、 2.4’
−ジヒドロキシジフェニルメタン、2.2−ジヒドロキ
シジフェニルメタン及び若干の多核体で、ジヒドロキシ
ジフェニルメタン混合体の4.4一体の含有率は80.
2%であり、 2.4°一体は19.8%、 2.2一
体は0.1%であった。When the reaction mixture was cooled to room temperature and analyzed, no hydroxybenzyl alcohol was found in the reaction mixture, and the product was 4,4-dihydroxydiphenylmethane, 2.4'
-dihydroxydiphenylmethane, 2.2-dihydroxydiphenylmethane and some polynuclear bodies, the content of 4.4 units in the dihydroxydiphenylmethane mixture is 80.
2%, 2.4° integral was 19.8%, and 2.2 integral was 0.1%.
比較例!
15m1の密閉式耐圧ガラス反応器にイソプロピルアル
コール5sj、フェノール0.515g 15.47
ミリモル)及び水酸化ナトリウム0.230g (5,
47ミリモル)を入れ、窒素で置換した後に80℃で加
熱攪拌し、内容物が溶けたのを確認して温度を室温にま
でもどした。Comparative example! 5sj of isopropyl alcohol and 0.515g of phenol in a 15ml closed pressure glass reactor 15.47
mmol) and sodium hydroxide 0.230 g (5,
After purging with nitrogen, the mixture was heated and stirred at 80°C, and after confirming that the contents had melted, the temperature was returned to room temperature.
昇華精製したバラホルムアルデヒドをイソプロピルアル
コールに溶かした濃度が0.67モル/βの純粋へミホ
ルマールイソブロビルアルコール0.82鵬I(ホルム
アルデヒド0.547ミリモル)を加え、再び窒素で置
換し50℃で9時間加熱撹拌した。この反応混液を室温
にもどし液体クロマトグラフィーで分析したところ、生
成物はパラヒドロキシベンジルアルコールとオルトヒド
ロキシベンジルアルコールの二種類で、パラヒドロキシ
ベンジルアルコールの選択率は40.3%であった。Pure hemiformal isobrobyl alcohol 0.82 Peng I (formaldehyde 0.547 mmol) with a concentration of 0.67 mol/β was added, and the mixture was purged with nitrogen again and heated at 50°C. The mixture was heated and stirred for 9 hours. When this reaction mixture was returned to room temperature and analyzed by liquid chromatography, it was found that there were two types of products, parahydroxybenzyl alcohol and orthohydroxybenzyl alcohol, and the selectivity for parahydroxybenzyl alcohol was 40.3%.
次いでこの反応液に12N−HGiを加え、0.05モ
ルの酸が過剰になるように調整し、窒素置換してから8
0℃で4時間加熱撹拌した。Next, 12N-HGi was added to this reaction solution, adjusted to have an excess of 0.05 mol of acid, and the mixture was replaced with nitrogen.
The mixture was heated and stirred at 0°C for 4 hours.
反応液を室温にもどし分析したところ反応液中にはヒド
ロキシベンジルアルコールは認められず、生成物は、
4.4’−ジヒドロキシジフェニルメタン、2.4−
ジヒドロキシジフェニルメタン、2.2゛−ジヒドロキ
シジフェニルメタン及び若干の多核体であった。ジヒド
ロキシジフェニルメタン混合体中の4.4一体の含有率
は36.1%であり。When the reaction solution was returned to room temperature and analyzed, no hydroxybenzyl alcohol was found in the reaction solution, and the product was
4.4'-dihydroxydiphenylmethane, 2.4-
They were dihydroxydiphenylmethane, 2.2'-dihydroxydiphenylmethane, and some polynuclear substances. The content of 4.4 in the dihydroxydiphenylmethane mixture was 36.1%.
2.4゛一体は57.7%、 2,2゛一体は6.2%
であった。2.4゛ one-piece 57.7%, 2,2゛ one-piece 6.2%
Met.
実施例2
15m1の密閉式耐圧ガラス反応器にイソプロピルアル
コール5s1、フェノール0.497g+5.28 ミ
リモル)、水酸化ナリウム0.222g (5,28ミ
リモル)及び18−クラウン−6−エーテル1.840
g!5.28ミリモル)を入れ、窒素置換後80℃で加
熱撹拌し、内容物が溶けたのを確認して温度を室1品に
もどした。Example 2 In a 15 ml closed pressure glass reactor, 5 sl of isopropyl alcohol, 0.497 g phenol (0.497 g + 5.28 mmol), 0.222 g (5.28 mmol) sodium hydroxide and 1.840 g 18-crown-6-ether
g! After purging with nitrogen, the mixture was heated and stirred at 80°C, and after confirming that the contents had melted, the temperature was returned to the original temperature in the chamber.
昇華精製したバラホルムアルデヒドをイソプロピルアル
コールに溶かした濃度が0.67モル/!の純粋へミホ
ルマール・イソプロピルアルコール溶液1.58a+1
(ホルムアルデヒド!、06ミリモル)を加え、再び
窒素置換し40℃で92時間加熱撹拌し、第一段目の反
応を終えた。The concentration of rose formaldehyde purified by sublimation dissolved in isopropyl alcohol is 0.67 mol/! Pure hemiformal isopropyl alcohol solution 1.58a+1
(Formaldehyde!, 06 mmol) was added, the atmosphere was replaced with nitrogen again, and the mixture was heated and stirred at 40° C. for 92 hours to complete the first stage reaction.
反応液中の生成物はパラヒドロキシベンジルアルコール
、オルトヒド口キシベンジルアルコール、ジメチロール
フェノールの三種で、三種類中のパラヒドロキシベンジ
ルアルコールの比率は86.1%、モノメチロール化に
おけるパラ選択性は88.1%、ホルムアルデヒド転化
率は100%であった。The products in the reaction solution are three types: parahydroxybenzyl alcohol, orthohydroxybenzyl alcohol, and dimethylolphenol. The ratio of parahydroxybenzyl alcohol among the three types is 86.1%, and the paraselectivity in monomethylolation is 88. .1%, and the formaldehyde conversion rate was 100%.
この反応混液にフェノール0.992g (10,54
ミリモル) 、 12N−11c10.45+++11
5.40ミリモル)を加え、窒素置換した後、60℃で
7時間加熱撹拌した1反応液を室温までもどし分析した
ところ、反応液中にはヒドロキシベンジルアルコールは
認められず、生成物は4.4°−ジヒドロキシジフェニ
ルメタン、 2.4−ジヒドロキシジフェニルメタン。This reaction mixture was added with 0.992 g of phenol (10,54
mmol), 12N-11c10.45+++11
After adding 5.40 mmol) and purging with nitrogen, the reaction solution was heated and stirred at 60°C for 7 hours. When the reaction solution was returned to room temperature and analyzed, no hydroxybenzyl alcohol was observed in the reaction solution, and the product was 4.40 mmol). 4°-dihydroxydiphenylmethane, 2.4-dihydroxydiphenylmethane.
2.2゛−ジヒドロキシジフェニルメタン及び芳香族環
を3つ以上含む若干の多核体であり、ジヒドロキシジフ
ェニルメタンの選択率は92.3%、またジヒドロキシ
ジフェニルメタン類の異性体比は4.4′一体が81.
1%、 2.4一体が17.3%、 2.2°−体が1
.6%であった6
〔発明の効果1
本発明は、フェノールとホルムアルデヒドからジヒドロ
キシジフェニルメタンを合成する方法において、第一段
反応として塩基性条件下、アルコール系有機溶媒を用い
、かつクラウンエーテルを加えることによりパラヒドキ
シベンジルアルコールを選択的に合成する工程を介する
ことにより、4.4°一体を選択的に製造することがで
きた。2.2'-dihydroxydiphenylmethane and some polynuclear substances containing three or more aromatic rings, the selectivity of dihydroxydiphenylmethane is 92.3%, and the isomer ratio of dihydroxydiphenylmethane is 4.4' and 81' ..
1%, 2.4 body is 17.3%, 2.2°-body is 1
.. [Effect of the invention 1] The present invention is a method for synthesizing dihydroxydiphenylmethane from phenol and formaldehyde, in which an alcoholic organic solvent is used under basic conditions and a crown ether is added as the first step reaction. Through the process of selectively synthesizing parahydroxybenzyl alcohol, it was possible to selectively produce 4.4° monomer.
本発明は新規な4.4−ジヒドロキシジフェニルメタン
の製造方法であり、これによって、 4.4’−ジヒド
ロキシジフェニルメタンを高収率で得ることができる。The present invention is a novel method for producing 4,4-dihydroxydiphenylmethane, whereby 4,4'-dihydroxydiphenylmethane can be obtained in high yield.
Claims (1)
キシジフェニルメタンを製造する方法において、フェノ
ールとホルムアルデヒド源とを、アルコール系有機溶媒
中、塩基性条件下で、クラウンエーテルを加えて反応さ
せてパラヒドロキシベンジルアルコールを生成させ、次
いで反応液を酸性化し、更にフェノールを反応させるこ
とを特徴とする4,4′−ジヒドロキシジフェニルメタ
ンの製造方法。(1) In a method for producing dihydroxydiphenylmethane from phenol and a formaldehyde source, phenol and a formaldehyde source are reacted in an alcoholic organic solvent under basic conditions with the addition of crown ether to produce parahydroxybenzyl alcohol. A method for producing 4,4'-dihydroxydiphenylmethane, which is characterized in that the reaction solution is acidified, and further phenol is reacted.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24673089A JPH03109342A (en) | 1989-09-22 | 1989-09-22 | Production of 4,4'-dihydroxydiphenylmethane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24673089A JPH03109342A (en) | 1989-09-22 | 1989-09-22 | Production of 4,4'-dihydroxydiphenylmethane |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03109342A true JPH03109342A (en) | 1991-05-09 |
Family
ID=17152796
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24673089A Pending JPH03109342A (en) | 1989-09-22 | 1989-09-22 | Production of 4,4'-dihydroxydiphenylmethane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03109342A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06211715A (en) * | 1993-01-22 | 1994-08-02 | Mitsui Toatsu Chem Inc | Production of bisphenol f |
US6718132B2 (en) | 2001-10-30 | 2004-04-06 | Ricoh Company, Ltd. | Zoom lens, camera apparatus and portable information terminal apparatus |
JP2006008634A (en) * | 2004-06-29 | 2006-01-12 | Nippon Steel Chem Co Ltd | Method for producing bisphenols |
JP2007111857A (en) * | 2006-12-19 | 2007-05-10 | Shinji Yokoshima | Lightweight chargeable, motor-driven tool with drop preventive function |
CN113214059A (en) * | 2021-02-09 | 2021-08-06 | 山东新和成药业有限公司 | Preparation method of raspberry ketone |
-
1989
- 1989-09-22 JP JP24673089A patent/JPH03109342A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06211715A (en) * | 1993-01-22 | 1994-08-02 | Mitsui Toatsu Chem Inc | Production of bisphenol f |
US6718132B2 (en) | 2001-10-30 | 2004-04-06 | Ricoh Company, Ltd. | Zoom lens, camera apparatus and portable information terminal apparatus |
JP2006008634A (en) * | 2004-06-29 | 2006-01-12 | Nippon Steel Chem Co Ltd | Method for producing bisphenols |
JP2007111857A (en) * | 2006-12-19 | 2007-05-10 | Shinji Yokoshima | Lightweight chargeable, motor-driven tool with drop preventive function |
CN113214059A (en) * | 2021-02-09 | 2021-08-06 | 山东新和成药业有限公司 | Preparation method of raspberry ketone |
CN113214059B (en) * | 2021-02-09 | 2022-10-04 | 山东新和成药业有限公司 | Preparation method of raspberry ketone |
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