JPH01265051A - Production of diaryloxyalkane - Google Patents
Production of diaryloxyalkaneInfo
- Publication number
- JPH01265051A JPH01265051A JP63092055A JP9205588A JPH01265051A JP H01265051 A JPH01265051 A JP H01265051A JP 63092055 A JP63092055 A JP 63092055A JP 9205588 A JP9205588 A JP 9205588A JP H01265051 A JPH01265051 A JP H01265051A
- Authority
- JP
- Japan
- Prior art keywords
- chloride
- mol
- water
- aromatic alcohol
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- -1 aryloxyalkyl halide Chemical class 0.000 claims abstract description 11
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 6
- VQUYNUJARXBNPK-UHFFFAOYSA-N 2-chloroethoxybenzene Chemical compound ClCCOC1=CC=CC=C1 VQUYNUJARXBNPK-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 abstract description 3
- 150000007522 mineralic acids Chemical group 0.000 abstract description 2
- 125000001624 naphthyl group Chemical group 0.000 abstract description 2
- 150000007524 organic acids Chemical group 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract 2
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 229910052740 iodine Inorganic materials 0.000 abstract 1
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- OIZMZUUFHOZQIT-UHFFFAOYSA-N 1-(2-chloroethoxy)-3-methylbenzene Chemical compound CC1=CC=CC(OCCCl)=C1 OIZMZUUFHOZQIT-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- DFJCCNZMGVNBKQ-UHFFFAOYSA-N 1-chloro-4-(2-chloroethoxy)benzene Chemical compound ClCCOC1=CC=C(Cl)C=C1 DFJCCNZMGVNBKQ-UHFFFAOYSA-N 0.000 description 1
- QPDSALLMZSDJIM-UHFFFAOYSA-M 1-dodecyl-4-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=C(C)C=C1 QPDSALLMZSDJIM-UHFFFAOYSA-M 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- MSIGTXLXMVOOQD-UHFFFAOYSA-N 2-phenoxyethyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCCOC1=CC=CC=C1 MSIGTXLXMVOOQD-UHFFFAOYSA-N 0.000 description 1
- AZXLOLRTEJEZHJ-UHFFFAOYSA-N 3-chloropropoxybenzene Chemical compound ClCCCOC1=CC=CC=C1 AZXLOLRTEJEZHJ-UHFFFAOYSA-N 0.000 description 1
- JKXCPAVECBFBOC-UHFFFAOYSA-N 4-chlorobutoxybenzene Chemical compound ClCCCCOC1=CC=CC=C1 JKXCPAVECBFBOC-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 1
- GEHMWSIEKHOKJZ-UHFFFAOYSA-M benzyl(trioctyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CC1=CC=CC=C1 GEHMWSIEKHOKJZ-UHFFFAOYSA-M 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- GIDDQKKGAYONOU-UHFFFAOYSA-N octylazanium;bromide Chemical compound Br.CCCCCCCCN GIDDQKKGAYONOU-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の分野）
本発明は記録オ料用の熱可融性物質として有用なジアリ
ールオキシアルカンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to a method for producing diaryloxyalkanes useful as thermofusible materials for recording materials.
（従来技術）
ジアリールオキシアルカンの製造方法としては従来より
、１）アリールオキシアルコールの活性エステルとフェ
ノールを反応させる方法、２）アルキレンジオールのジ
活性エステルとフェノールを反応させる方法、３）アリ
ールオキシアルキルハライドとフェノールを塩基存在下
に反応させる方法、４）ウィリアムソン法等がしられて
おり。(Prior Art) Conventional methods for producing diaryloxyalkanes include 1) a method of reacting an active ester of an aryloxyalcohol with phenol, 2) a method of reacting a diactive ester of an alkylene diol with phenol, and 3) a method of reacting an aryloxyalkyl A method of reacting a halide and phenol in the presence of a base, 4) Williamson method, etc. are known.
特開昭６２−２８１８３６号、特公昭５１−３３５４２
号等に開示されている。しかしながらこれらの方法では
、収率が低かったり、ハンドリングの点、コストの点、
安全性の点などで問題があった。JP 62-281836, JP 51-33542
Disclosed in the issue etc. However, these methods have low yields, handling issues, cost issues,
There were problems with safety and other issues.
（発明の目的）
本発明の目的は高収率で、しかも精製が容易でかつ低コ
ストなジアリールオキシアルカンの製造方法を提供する
ことである。(Objective of the Invention) An object of the present invention is to provide a method for producing diaryloxyalkanes with high yield, easy purification, and low cost.
（発明の構成）
本発明の目的は、アリールオキシアルキルハライドと芳
香族アルコールを相間移動触媒の存在下で反応させるこ
とを特徴とするジアリールオキシアルカンの製造方法を
開発することにより達成された。(Structure of the Invention) The object of the present invention was achieved by developing a method for producing diaryloxyalkanes, which is characterized by reacting an aryloxyalkyl halide and an aromatic alcohol in the presence of a phase transfer catalyst.
本発明に係わるアリールオキシアルキルハライドは下記
一般式（１）で表されるものを言う。The aryloxyalkyl halide according to the present invention is represented by the following general formula (1).
Ａｒ０ＣＩ、Ｈ２，ＩＸ （Ｉ）上式中、Ａｒ
は置換基を有していても良いフェニル基又はナフチル基
を、Ｘはハロゲン原子、好ましくは塩素原子又は臭素原
子を、ｎは２〜１０の整数を表す。Ar0CI, H2, IX (I) In the above formula, Ar
represents a phenyl group or a naphthyl group which may have a substituent, X represents a halogen atom, preferably a chlorine atom or a bromine atom, and n represents an integer of 2 to 10.
Ａｒの置換基の例としてはアルキル基、アルコキシ基、
ハロゲン原子、ニトロ基、シアノ基、アシル基、フェニ
ル基１等があげられる。Examples of substituents for Ar include alkyl groups, alkoxy groups,
Examples include a halogen atom, a nitro group, a cyano group, an acyl group, and a phenyl group.
具体的な例としては、２−フェノキシエチルクロリド、
３−フェノキシプロビルクロリド、４−フェノキシブチ
ルクロリド、６−フェノキシエチルクロリド、１０−フ
ェノキシデシルクロリド。Specific examples include 2-phenoxyethyl chloride,
3-phenoxypropyl chloride, 4-phenoxybutyl chloride, 6-phenoxyethyl chloride, 10-phenoxydecyl chloride.
２−Ｐ−メチルフェノキシエチルクロリド、２−Ｐ−エ
チルフェノキシエチルクロリド、２−Ｐ−メトキシフェ
ノキシエチルクロリド、２−Ｐ−エトキシフェノキシエ
チルクロリド、２−ｐ−クロロフェノキシエチルクロリ
ド、２−ｍ−メチルフェノキシエチルクロリド、２−０
−メチルフェノキシエチルクロリド、２−β−ナフチル
オキンエチルクロリド、２−β−ナフチルオキシプロピ
ルクロリド、３−β−ナフチルオキシプロピル−２−ク
ロリド１等が挙げられる。これらのなかでも特に、β−
アリールオキシエチルクロリドとくに。2-P-methylphenoxyethyl chloride, 2-P-ethylphenoxyethyl chloride, 2-P-methoxyphenoxyethyl chloride, 2-P-ethoxyphenoxyethyl chloride, 2-p-chlorophenoxyethyl chloride, 2-m-methyl Phenoxyethyl chloride, 2-0
-methylphenoxyethyl chloride, 2-β-naphthyloxyneethyl chloride, 2-β-naphthyloxypropyl chloride, 3-β-naphthyloxypropyl-2-chloride 1, and the like. Among these, β-
Especially aryloxyethyl chloride.
原料の人手のしやすさから、２−フェノキシエチルクロ
リドが好ましい。2-phenoxyethyl chloride is preferred from the viewpoint of easy handling of raw materials.
本発明に係わる製造方法では、Ｘが反応性の低い塩素原
子の場合でも反応が円滑に進行するという利点がある。The production method according to the present invention has the advantage that the reaction proceeds smoothly even when X is a chlorine atom with low reactivity.
本発明に係わる芳香族アルコールは、低級アルキル基、
低級アルコキシ基、ハロゲン原子などの置換基を有して
いてもよい、フェノール又はナフトール誘導体を言い、
具体的にはフェノール、ｐ。The aromatic alcohol according to the present invention includes a lower alkyl group,
Refers to a phenol or naphthol derivative that may have a substituent such as a lower alkoxy group or a halogen atom,
Specifically, phenol, p.
ｍ、又は０−クレゾール、ｐ、ｍ、又は０−エチルフェ
ノール、ｐ、ｍ又は ０−プロピルフェノール、ｐ、ｍ
、又は０−メトキシフェノール、ｐ。m, or 0-cresol, p, m, or 0-ethylphenol, p, m, or 0-propylphenol, p, m
, or 0-methoxyphenol, p.
ｍ、又はＱ−エトキシフェノール、ｐ、ｍ、又は０−ク
ロロフェノール、α−ナフトール、β−ナフトールなど
があげられる。Examples include m- or Q-ethoxyphenol, p-, m- or 0-chlorophenol, α-naphthol, β-naphthol, and the like.
本発明に係わる相間移動触媒としては、４級アンモニウ
ム塩、ポリアルキレングリコール、クラウンエーテルな
どがあげられるが、この中で特に。Examples of the phase transfer catalyst according to the present invention include quaternary ammonium salts, polyalkylene glycols, crown ethers, etc. Among these, in particular.
下記一般式（ＩＩ）で表される４級アンモニウム塩が好
ましい。A quaternary ammonium salt represented by the following general formula (II) is preferred.
上式中、Ｒ１〜Ｒ１はアルキル基又はアリール基を、Ｘ
は無機酸又は有機酸の残基９例えばＣＩ。In the above formula, R1 to R1 represent an alkyl group or an aryl group,
is a residue of an inorganic or organic acid 9 such as CI.
Ｂｒ、ｒ、０３Ｏｚ Ｒ，（Ｒは○Ｈ，アリール基。Br, r, 03Oz R, (R is ○H, aryl group.
０ＮＲＩ Ｒ２Ｒｉ Ｒ−を表す、）などの酸基を表
す。0NRI R2Ri R- represents an acid group such as ).
４級アンモニウム塩の具体的な例としては、臭化テトラ
メチルアンモニウム、臭化テトラエチルアンモニウム、
臭化テトラ−ｎ−ブチルアンモニウム、臭化テトラ−ｎ
−オクチルアンモニウム。Specific examples of quaternary ammonium salts include tetramethylammonium bromide, tetraethylammonium bromide,
Tetra-n-butylammonium bromide, Tetra-n bromide
-Octylammonium.
塩化テトラ−ｎ−ブチルアンモニウム、塩化テトラエチ
ルアンモニウム、塩化トリエチルベンジルアンモニウム
、臭化トリエチルベンジルアンモニウム、塩化トリオク
チルベンジルアンモニウム。Tetra-n-butylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylbenzylammonium chloride.
臭化トリオクチルベンジルアンモニウム、塩化トリブチ
ルベンジルアンモニウム、臭化トリフチルベンジルアン
モニウム、塩化Ｎ−ラウリルピリジニウム、水酸化テト
ラエチルアンモニウム、水酸化トリエチルベンジルアン
モニウム、臭化トリメチルフェニルアンモニウム、テト
ラ−ｎ−ブチルアンモニウムハイドロジエンサルフェー
ト、Ｎ−ペンジルピコリウムクロライド、ヨウ化テトラ
エチルアンモニウム、ヨウ化テトラ−ｎ−ブチルアンモ
ニウム、Ｎ−ラウリル−４−ピコリニウムクロリド等が
あげられる。trioctylbenzylammonium bromide, tributylbenzylammonium chloride, triphthylbenzylammonium bromide, N-laurylpyridinium chloride, tetraethylammonium hydroxide, triethylbenzylammonium hydroxide, trimethylphenylammonium bromide, tetra-n-butylammonium hydrodiene Sulfate, N-pendylpicolium chloride, tetraethylammonium iodide, tetra-n-butylammonium iodide, N-lauryl-4-picolinium chloride, and the like.
４級アンモニウム塩の使用量はアリ−レオキンアルキル
ハライド１モルに対して０．０１〜３モルが好ましく、
特に０．１〜１モルが好ましい。The amount of quaternary ammonium salt used is preferably 0.01 to 3 mol per 1 mol of aryleoquine alkyl halide,
Particularly preferred is 0.1 to 1 mol.
アリールオキシアルキルハライドと芳香族アルコールの
使用量は、アリールオキシアルキル７％ライド１モルに
対して、芳香族アルコール０．５〜２モルが好ましく、
特に０．９〜１．２モ′ルが好ましい。The amount of aryloxyalkyl halide and aromatic alcohol used is preferably 0.5 to 2 mol of aromatic alcohol per 1 mol of aryloxyalkyl 7% ride.
Particularly preferred is 0.9 to 1.2 mol.
本発明の製造方法を実施する際の反応温度は４０〜１２
０°Ｃが好ましく、特に６０〜１００゜Ｃが好ましい、
１３０°Ｃ以上だと副反応が生じやすく、高純度の生成
物を得にくい。The reaction temperature when carrying out the production method of the present invention is 40 to 12
0°C is preferred, particularly 60 to 100°C.
If the temperature is 130°C or higher, side reactions are likely to occur, making it difficult to obtain a highly pure product.
本発明の製造方法を実施する際には、水、水と有機溶媒
の混合物または有機溶媒中で行うことができるが、特に
４級アンモニウム塩の溶鯉性及びコストの点から水、又
は水と有機溶媒の混合物中で行うことがこのましい。When carrying out the production method of the present invention, it can be carried out in water, a mixture of water and an organic solvent, or an organic solvent. Preferably, the reaction is carried out in a mixture of organic solvents.
本発明の製造方法を実施する際には、塩基を併用するこ
とが好ましく、塩基としてはナトリウム化合物、または
カリウム化合物が好ましい。When carrying out the production method of the present invention, it is preferable to use a base in combination, and the base is preferably a sodium compound or a potassium compound.
塩基の具体例としては、苛性ソーダ、苛性カリ。Specific examples of bases include caustic soda and caustic potash.
炭酸ソーダ、炭酸カリ等があげられる。この中で特に苛
性ソーダ、苛性カリが好ましい。Examples include carbonated soda and carbonated potassium. Among these, caustic soda and caustic potash are particularly preferred.
使用する塩基の中は芳香族アルコール１モルに対して１
〜３モルが好ましく、特に１〜２モルが好ましい。The base used is 1 mole of aromatic alcohol.
-3 mol is preferable, and 1-2 mol is especially preferable.
不発明の製造方法を実施する際には、ハンドリングの点
から仕込み時の固形分濃度が５０％以下であることが好
ましい。When implementing the uninvented manufacturing method, it is preferable that the solid content concentration at the time of preparation is 50% or less from the viewpoint of handling.
また不活性ガスの＝囲気下に反応を行うことも。The reaction can also be carried out under an atmosphere of inert gas.
生成物の着色防止の点から好ましい。This is preferable from the viewpoint of preventing coloring of the product.
本発明に係わる製造方法は収率が極めて良好な上、生成
物の着色が少なく、かつハンドリングが容易であること
などすぐれた点が多い。The production method according to the present invention has many advantages such as a very good yield, less coloring of the product, and ease of handling.
（発明の実施例） 以下実施例により本発明を具体的に説明するが。(Example of the invention) The present invention will be specifically explained below with reference to Examples.
本発明は実施例に限定されるものではない。The invention is not limited to the examples.
実施例１
１．２−ジフェノキシエタン
かきまぜ機のついた三つロフラスコに、２−フェノキン
エチルクロリド１．０モル、フェノール１．０モル、苛
性ソーダ２．０モル、臭化ｆト５− ｎ −ブチルアン
モニウム０．３モルｌｋｌｏＯｍｌを秤りとる。かきま
ぜなから８０’Ｃで３時間反応させた９反応混合物を水
にあけ、析出した結晶をろ取し、さらに水およびメタノ
ール水で洗浄し目的物を得た。収率９８％、融点９８°
Ｃ比較例１
かきまぜ機のついた三つロフラスコに、２−フェノキシ
エチルクロリド１．０モル、フェノール１、Ｑ％ル、前
件ソーダ２．Ｑ％ル、水１００ｍ１を秤りとり、かきま
ぜなから８０’Ｃで３時間反応させた。実施例１と同様
に後処理して目的物を得た。収＄＝３０％、融点９６〜
９８°Ｃ比較例２
かきまぜ機のついた三つロフラスコに、２−フェノキシ
エチルトシレート１．０モル、フェノール１．０モル、
苛性ソーダ２．０モル、水１００ｍ１を秤りとり、かき
まぜながら８０°Ｃで３時間反応させた。実施例１と同
様に後処理して目的物を得た。収率９０％、融点９８°
Ｃ
実施例２
■−フェノキンー２−ｐ−エチルフェノキシエタン
かきまぜ機のついた三つロフラスコに、２−フェノキン
エチルクロリド１．０モル、ｐ−エチルフェノール１．
０モル、苛性ソータ２ 、 ［１モル。Example 1 1.2-Diphenoxyethane In a three-neck flask equipped with a stirrer, 1.0 mol of 2-phenoquinethyl chloride, 1.0 mol of phenol, 2.0 mol of caustic soda, and 5-n bromide were added. - Weigh out 0.3 mol lkloOml of butylammonium. 9. The reaction mixture was reacted at 80'C for 3 hours without stirring and poured into water, and the precipitated crystals were collected by filtration and further washed with water and methanol to obtain the desired product. Yield 98%, melting point 98°
C Comparative Example 1 In a three-necked flask equipped with a stirrer, 1.0 mol of 2-phenoxyethyl chloride, 1 mol of phenol, 1.0 mol of phenol, 2. 100 ml of water was weighed out and reacted at 80'C for 3 hours without stirring. The desired product was obtained by post-treatment in the same manner as in Example 1. Yield: $30%, melting point: 96~
98°C Comparative Example 2 In a three-neck flask equipped with a stirrer, 1.0 mol of 2-phenoxyethyl tosylate, 1.0 mol of phenol,
2.0 mol of caustic soda and 100 ml of water were weighed out and reacted at 80°C for 3 hours while stirring. The desired product was obtained by post-treatment in the same manner as in Example 1. Yield 90%, melting point 98°
C Example 2 ■-Fenoquine-2-p-ethylphenoxyethane In a three-necked flask equipped with a stirrer, 1.0 mol of 2-phenoquine ethyl chloride and 1.0 mol of p-ethylphenol were added.
0 mol, caustic sorter 2, [1 mol.
Ａ化テトラ−ｎ−ブチルアンモニウム０．３モル。Tetra-n-butylammonium A 0.3 mol.
水１００ｍ１を秤りとり、かきまぜながら８０’Ｃで３
時間反応させた、実施例１と同様に後処理して目的物を
得た。収率９６％、融点１０６°Ｃ実施例３
■、２−ジーｍ−メチルフェノキ／エタンかきまぜ機の
ついた三つロフラスコに、２−ｍ−メチルフェノキシエ
チルクロリド１．０モル。Weigh out 100ml of water and heat it to 80'C while stirring.
The desired product was obtained by post-treatment in the same manner as in Example 1, in which the reaction was carried out for a period of time. Yield 96%, melting point 106 DEG C. Example 3 (1) 1.0 mol of 2-m-methylphenoxyethyl chloride was placed in a three-necked flask equipped with a 2-di-m-methylphenoxy/ethane stirrer.
ｍ−メチルフェノール１．０モル、苛性ソーダ２゜０モ
ル、臭化テトラ−ｎ−ブチルアンモニウム０゜３モル、
水１００ｍ１を秤りとり、かきまぜながら９０°Ｃで３
時間反応させた。実施例１と同様に後処理して目的物を
得た。収率９５％、融点９８°Ｃ
実施例４〜９
実施例１と同様にして以下の芳香族アルコールを反応さ
せた。1.0 mol of m-methylphenol, 2.0 mol of caustic soda, 0.3 mol of tetra-n-butylammonium bromide,
Weigh out 100ml of water and heat it to 90°C while stirring.
Allowed time to react. The desired product was obtained by post-treatment in the same manner as in Example 1. Yield 95%, melting point 98°C Examples 4 to 9 The following aromatic alcohols were reacted in the same manner as in Example 1.
実施例４ ４−クレゾール
Ｘ絶倒５ ４−イソプロピルフェノール実Ｍ例６
３．４−ジメチルフェノール実施例７ ４−フロロフェ
ノール
実施例８ ４−クロロフェノール
実施例９ ４−メトキンフェノール
実施例１と同様に後処理して
１ｉ例４ １−フェノキン−２−ｐ−メチルフェノキン
エタン（融点１００°Ｃ）、実施例５１−フェノキシ−
２−ｐ−イソプロピルフェノキシエタン（融点 ９５°
Ｃ）、実施例６１−フニノキン−２（３，４−ジメチル
フェノキシ）エタン（融点１００°Ｃ）、 実施例７１
−フェノキシ−２−ｐ−フロロフェノキシエタン（融点
９０°Ｃ）、実施例８１−フェノキン−２−ｐ−クロ
ロフェノキシエタン（融点１０１°Ｃ）、実施例９１−
フェノキシ−２−ｐ−メトキシフェノキンエタン（融点
１０２°Ｃ）を得た。いずれも収率は９０％以上だった
。Example 4 4-Cresol
3. 4-Dimethylphenol Example 7 4-Fluorophenol Example 8 4-Chlorophenol Example 9 4-Methoquinphenol After treatment in the same manner as Example 1, 1i Example 4 1-phenoquine-2-p-methyl Phenoquinethane (melting point 100°C), Example 51-phenoxy-
2-p-isopropylphenoxyethane (melting point 95°
C), Example 61-funinoquine-2(3,4-dimethylphenoxy)ethane (melting point 100°C), Example 71
-Phenoxy-2-p-chlorophenoxyethane (melting point 90°C), Example 81-phenoquine-2-p-chlorophenoxyethane (melting point 101°C), Example 91-
Phenoxy-2-p-methoxyphenoquinethane (melting point 102°C) was obtained. In all cases, the yield was over 90%.
Claims (1)
相間移動触媒の存在下で反応させることを特徴とするジ
アリールオキシアルカンの製造方法A method for producing a diaryloxyalkane, which comprises reacting an aryloxyalkyl halide and an aromatic alcohol in the presence of a phase transfer catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63092055A JPH01265051A (en) | 1988-04-14 | 1988-04-14 | Production of diaryloxyalkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63092055A JPH01265051A (en) | 1988-04-14 | 1988-04-14 | Production of diaryloxyalkane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01265051A true JPH01265051A (en) | 1989-10-23 |
Family
ID=14043817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63092055A Pending JPH01265051A (en) | 1988-04-14 | 1988-04-14 | Production of diaryloxyalkane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01265051A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002090351A1 (en) * | 1999-11-24 | 2002-11-14 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivative |
| EP1311485A1 (en) * | 2000-08-14 | 2003-05-21 | Teva Pharmaceutical Industries Ltd. | Processes for preparing cilostazol |
| US6630590B1 (en) | 1999-11-24 | 2003-10-07 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivatives |
| WO2004024716A1 (en) * | 2002-09-10 | 2004-03-25 | Otsuka Pharmaceutical Co., Ltd. | Process for producing cilostazol |
| US7399864B2 (en) | 2001-05-02 | 2008-07-15 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivatives |
| US7825251B2 (en) | 2001-05-02 | 2010-11-02 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivatives |
-
1988
- 1988-04-14 JP JP63092055A patent/JPH01265051A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002090351A1 (en) * | 1999-11-24 | 2002-11-14 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivative |
| US6630590B1 (en) | 1999-11-24 | 2003-10-07 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivatives |
| EP1311485A1 (en) * | 2000-08-14 | 2003-05-21 | Teva Pharmaceutical Industries Ltd. | Processes for preparing cilostazol |
| EP1311485A4 (en) * | 2000-08-14 | 2004-05-12 | Teva Pharma | Processes for preparing cilostazol |
| US7399864B2 (en) | 2001-05-02 | 2008-07-15 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivatives |
| US7825251B2 (en) | 2001-05-02 | 2010-11-02 | Otsuka Pharmaceutical Co., Ltd. | Process for producing carbostyril derivatives |
| WO2004024716A1 (en) * | 2002-09-10 | 2004-03-25 | Otsuka Pharmaceutical Co., Ltd. | Process for producing cilostazol |
| US7026486B2 (en) | 2002-09-10 | 2006-04-11 | Otsuka Pharmaceutical Co., Ltd. | Process for production cilostazol |
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