JPS62246568A - Crown ether compound and production thereof - Google Patents
Crown ether compound and production thereofInfo
- Publication number
- JPS62246568A JPS62246568A JP9078386A JP9078386A JPS62246568A JP S62246568 A JPS62246568 A JP S62246568A JP 9078386 A JP9078386 A JP 9078386A JP 9078386 A JP9078386 A JP 9078386A JP S62246568 A JPS62246568 A JP S62246568A
- Authority
- JP
- Japan
- Prior art keywords
- crown ether
- ether compound
- formula
- compound
- expressed
- 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
- -1 Crown ether compound Chemical class 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 7
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 abstract description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003063 flame retardant Substances 0.000 abstract description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野１
本発明は、新規なりラウンエーテル化合物、特に骨格中
に７リール基を有するクラウンエーテル化合物に関し、
及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a novel crown ether compound, particularly a crown ether compound having a 7-aryl group in its skeleton,
and its manufacturing method.
［従来の技術］
従来、シアノ７リールエーテル化合物は知られており、
その重合物は特開昭４７−１４２７０号公報。[Prior Art] Conventionally, cyano 7-aryl ether compounds have been known,
The polymer is disclosed in JP-A-47-14270.
特開昭５９−２０８４３３号公報により開示されている
。It is disclosed in Japanese Patent Application Laid-Open No. 59-208433.
しかしこれらの公報にはシアノアリールエーテルの環状
化合物、即ちクラウンエーテル化合物については何ら記
載されていない、しかしクラウンエーテルは環の構成原
子として非共有電子対酸素原子を有しているので、陽イ
オンを取り込んで錯化合物を形成しＫＯＨ，ｔ −Ｂｕ
ＯＫ等を有機溶媒に溶解したり、また光学分割試薬に
用いられ。However, these publications do not mention anything about cyclic compounds of cyanoaryl ethers, that is, crown ether compounds.However, crown ethers have a lone pair of oxygen atoms as ring constituent atoms, so they do not contain cations. KOH, t -Bu is incorporated to form a complex compound.
It is used to dissolve OK etc. in organic solvents and as an optical resolution reagent.
この他に有用な性質を持っている。従って有用な特性を
有するクラウンエーテル化合物が望まれている。It also has other useful properties. Therefore, crown ether compounds with useful properties are desired.
［発明が解決しようとする問題点］
本発明の目的は新規なりラウンエーテル化合物、及びそ
の製造方法を提供することにある。その為に本発明者等
はクラウンエーテル化合物、特にアリール基を構成要素
とするクラウンエーテル化合物を多年研究し、その結果
ベンゾニトリルとナフタレンとからなる新規なりラウン
エーテル化合物を得、これが難燃剤として有用な性質を
有することを見つけて本発明を達成したものである。[Problems to be Solved by the Invention] An object of the present invention is to provide a novel raw ether compound and a method for producing the same. To this end, the present inventors have spent many years researching crown ether compounds, especially crown ether compounds containing aryl groups as constituent elements, and as a result, they have obtained a new crown ether compound consisting of benzonitrile and naphthalene, which is useful as a flame retardant. The present invention was achieved by discovering that it has such properties.
［問題点を解決するための手段］
本発明のクラウンエーテル化合物は式１で示さまた。化
学式１で示されるクラウンエーテル化合物は、２．６−
ジハロゲノベンゾニトリルと２．７−シヒドロキシナフ
タレンのアルカリ金ＩＮ、塩とを中性極性溶媒中で反応
式Ｈの如く反応させることにより製造し得る。[Means for Solving the Problems] The crown ether compound of the present invention is represented by formula 1. The crown ether compound represented by chemical formula 1 is 2.6-
It can be produced by reacting dihalogenobenzonitrile and alkali gold IN, salt of 2,7-hydroxynaphthalene in a neutral polar solvent as shown in Reaction Formula H.
（ただし、又はハロゲン）
次に本発明の化学式Ｉに示されるクラウンエーテル化合
物の製造方法を詳述する０本発明に使用する２、８−ジ
ハロゲノベンゾニトリルは、 ２．８−ジクロロベンゾ
ニトリル、２．６−シフルオロベンゾニトリル等を挙げ
ることができる。(However, or halogen) Next, the method for producing the crown ether compound represented by the chemical formula I of the present invention will be described in detail. The 2,8-dihalogenobenzonitrile used in the present invention is 2,8-dichlorobenzonitrile, 2,6-cyfluorobenzonitrile and the like can be mentioned.
また、一方の２，７−シヒドロキシナフタレンのアルカ
リ金属塩としては、ナトリウム、カリウム、セシウム等
の塩を挙げることができるが、好ましい塩はナトリウム
、カリウム塩である。この２．７−シヒドロキシナフタ
レンのアルカリ塩を直接に２．８−ジハロゲノベンゾニ
トリルと反応させてもよく、またこの反応に際し２．７
−シヒドロキシナフタレンと炭酸や水酸化物のアル金属
化合物を同時に添加して反応を行なってもよい。Further, examples of the alkali metal salt of 2,7-hydroxynaphthalene include salts of sodium, potassium, cesium, etc., and preferred salts are sodium and potassium salts. This alkali salt of 2,7-dihydroxynaphthalene may be directly reacted with 2,8-dihalogenobenzonitrile, and in this reaction, 2,7
-The reaction may be carried out by simultaneously adding hydroxynaphthalene and an alkali metal compound such as carbonic acid or hydroxide.
また、本反応を中性極性溶媒中で行なう、この中性極性
溶媒とは、中性で、極性が大きく、炭素数が１〜４のア
ルコールおよび／または炭素数３〜７のケトンに対する
溶解性が高い有機溶剤であって、かつアルコール、ケト
ンではない有機溶媒である。なお、極性の大きい溶媒と
は、一般に誘電率および／または双極子モーメントが大
きい溶媒を言い、たとえば、誘電率が２０以上、双極子
モーメントが３．０デバイ以上のものは、通常、強極性
溶媒に含まれる。 このような有機溶剤として、ホルム
アミド、アセトアミド等のカルボン酸アミド類；Ｎ−メ
チルホルムアミド、Ｎ−エチルアセトアミド等のＮ−ア
ルキルカルボン類．Ｎ，Ｎ−ジメチルホルムアミド、
Ｎ，Ｎ−ジエチルホルムアミド、 Ｎ，Ｎ−ジメチルア
セトアミド等、Ｎ，Ｎ−ジアルキルカルボン酸アミド類
：２−ピロリドン等のラクタム類；Ｎ−メチルピロリド
ン、Ｎ−エチルピロリドン等のＮ−アルキルラクタム類
；ジメチルスルホキシド、ジエチルスルホキシド等のス
ルホキシド類；ジメチルスルホン、ジエチルスルホン、
ジフェニルスルホン等のスルホン類；アセトニトリル、
プロピオンニトリル、ブチロニトリル、スクシノニトリ
ル、ベンゾニトリル等のニトリル類等およびこれらの混
合物を挙げることができる。In addition, this reaction is carried out in a neutral polar solvent, which is neutral, highly polar, and has a solubility in alcohols having 1 to 4 carbon atoms and/or ketones having 3 to 7 carbon atoms. It is an organic solvent with a high alcohol content and is not an alcohol or ketone. Note that a highly polar solvent generally refers to a solvent with a large dielectric constant and/or dipole moment. For example, a solvent with a dielectric constant of 20 or more and a dipole moment of 3.0 Debye or more is usually a strong polar solvent. include. Examples of such organic solvents include carboxylic acid amides such as formamide and acetamide; N-alkyl carbonates such as N-methylformamide and N-ethylacetamide. N,N-dimethylformamide,
N,N-dialkylcarboxylic acid amides such as N,N-diethylformamide and N,N-dimethylacetamide; lactams such as 2-pyrrolidone; N-alkyllactams such as N-methylpyrrolidone and N-ethylpyrrolidone; Sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; dimethyl sulfone, diethyl sulfone,
Sulfones such as diphenylsulfone; acetonitrile,
Nitriles such as propionitrile, butyronitrile, succinonitrile, benzonitrile, etc., and mixtures thereof can be mentioned.
これらの様々の中性極性溶媒の中でも，ジメチルスルホ
キシド、ジメチルスルホン、ジエチルスルホン、ジフェ
ニルスルホン、スルホラン、Ｎ，Ｎ−ジメチルアセトア
ミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロ
リドン等の非プロトン性強極性有機溶媒およびそれらの
混合物が好ましく、スルホラン、Ｎ−メチルピロリドン
等が特に好ましい。Among these various neutral polar solvents, aprotic strongly polar solvents such as dimethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diphenyl sulfone, sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, etc. Organic solvents and mixtures thereof are preferred, with sulfolane, N-methylpyrrolidone and the like being particularly preferred.
次に本発明の反応条件について述べる。 ２．８−ジハ
ロゲノベンゾニトリルと２．７−ジヒドロキシナフタレ
ンのアルカリ金属との成分割合は任意のモル比で反応さ
せてもよいが、特に実質的に等モル比になるようにする
ことが好ましい、また、原料濃度は中性極性溶媒１ｆｔ
当りに対して２．６−ジハロゲノベンゾニトリルと２．
７−ジヒドロキシナフタレンのアルカリ金属塩とのモル
数和を２モル以下にすることが好ましい０反応温度は１
５０〜２５０℃の範囲で行なう、この反応条件で２．８
−ジハロゲノベンゾニトリルと２．７−ジヒドロキシナ
フタレンの金属塩とを１記の反応式■に従って反応させ
ると、ベンゾニトリルとナフタレンとを構成要素とする
上記の化学式１に示されるクラウンエーテル化合物が容
易に生成される。Next, the reaction conditions of the present invention will be described. The component proportions of 2.8-dihalogenobenzonitrile and the alkali metal of 2.7-dihydroxynaphthalene may be reacted at any molar ratio, but it is particularly preferable that they be in a substantially equimolar ratio. , and the raw material concentration is 1ft of neutral polar solvent.
2.6-dihalogenobenzonitrile and 2.
It is preferable that the sum of the moles of 7-dihydroxynaphthalene and the alkali metal salt is 2 moles or less. The reaction temperature is 1.
Under these reaction conditions, carried out in the range of 50 to 250°C, 2.8
- When dihalogenobenzonitrile and a metal salt of 2,7-dihydroxynaphthalene are reacted according to reaction formula (1), the crown ether compound shown in the above chemical formula 1 containing benzonitrile and naphthalene as constituent elements can be easily produced. is generated.
得られたクラウンエーテル化合物（化学式Ｉ）は従来知
られていない新規な化合物である。この環状のクラウン
エーテル化合物は白色の針状結晶の形態を取り得、きわ
めて安定な化合物であり、熱分解開始温度が約５２５℃
である。また、熱分解開始温度以下では、溶融せず、難
燃剤として有用性の高い化合物となる。また本化合物は
非共有電子対の酸素原子により陽イオンを選択的に取り
込み、安定な錯体を形成して化学反応的に興味ある特性
を有するものと期待される。The obtained crown ether compound (chemical formula I) is a novel compound that has not been previously known. This cyclic crown ether compound can take the form of white needle-shaped crystals and is an extremely stable compound, with a thermal decomposition onset temperature of approximately 525°C.
It is. Moreover, below the temperature at which thermal decomposition starts, it does not melt and becomes a highly useful compound as a flame retardant. Furthermore, this compound is expected to selectively take in cations using the lone pair of oxygen atoms, form a stable complex, and have interesting properties in terms of chemical reactions.
［発明の効果］
本発明方法により、２．８−ジハロゲノベンゾニトリル
と２．７−ジヒドロキシナフタレンのアルカリ金属塩と
反応させるという簡単な方法により。[Effects of the Invention] According to the method of the present invention, a simple method of reacting 2,8-dihalogenobenzonitrile with an alkali metal salt of 2,7-dihydroxynaphthalene.
ベンゾニトリルとナフタレンとを構成要素とする新規な
りラウンエーテル化合物を容易に製造できる。また得ら
るクラウンエーテル化合物は難燃剤として有用であり、
また錯体に形成されて化学反応の触媒、溶媒、成るいは
分析試薬、中間体等として有用である。A new raw ether compound containing benzonitrile and naphthalene as constituent elements can be easily produced. The resulting crown ether compound is also useful as a flame retardant,
It is also useful as a catalyst, solvent, analytical reagent, intermediate, etc. for chemical reactions when formed into a complex.
（実施例１）
攪拌装置および蒸留装置を備えた内容積３００ｒｎｌの
フラスコに２．６−シクロロベンゾニトリル５．１８ｇ
（０，０３モル）と２．７−シヒドロキシナフタレン
４．７５ｇ （０，０３モル）、及び炭酸カリウム４．
９７５ ｇ （０，０３８モル）、及び中性極性溶媒と
してのスルホラン１５０ｍｊＬ、生成水と共沸する溶媒
としてのトルエン５０ｍｊＬを入れた０次に不活性ガス
のアルゴンを吹き込み、アルゴンガス雰囲気下゛で攪拌
しながらｔｅｏ℃において２時間、次いで２００℃に昇
温して２．５時間反応を行なった。この反応によって生
成した固体生成物を濾別し、固体生成物を水中でブレン
ダー（ワーニング社製）で粉砕し、メタノールで洗浄後
、乾燥した０次に得られた固体粉体をＮ−メチルピロリ
ドン１２０ｍｊＬに溶解させ１次に冷却して白色の針状
結晶な生成した。更にこの針状結晶を濾別し、Ｎ−メチ
ルピロリドン、続いてアセトンで洗浄し、乾燥して精製
物を得た。このようにして得られた結晶体は２．１８ｇ
（収率２８％）であった。(Example 1) 5.18 g of 2,6-cyclobenzonitrile was placed in a flask with an internal volume of 300 rnl equipped with a stirring device and a distillation device.
(0.03 mol), 4.75 g (0.03 mol) of 2,7-hydroxynaphthalene, and 4.75 g (0.03 mol) of potassium carbonate.
975 g (0,038 mol), 150 mjL of sulfolane as a neutral polar solvent, and 50 mjL of toluene as a solvent that is azeotropic with the produced water were placed in a vacuum chamber, and argon, an inert gas, was blown into the reactor under an argon gas atmosphere. The reaction was carried out at teo° C. for 2 hours while stirring, and then heated to 200° C. for 2.5 hours. The solid product produced by this reaction was separated by filtration, the solid product was pulverized in water with a blender (manufactured by Warning), washed with methanol, and dried. It was dissolved in 120 mjL and cooled first to produce white needle-like crystals. Further, the needle-shaped crystals were filtered off, washed with N-methylpyrrolidone, then with acetone, and dried to obtain a purified product. The crystalline material thus obtained was 2.18 g.
(yield 28%).
この結晶体の物性値を測定した。マススペクトル分析に
よる分子量は５１８であった。また、元素分析の結果は
次の様であった。The physical properties of this crystal were measured. The molecular weight determined by mass spectrometry was 518. The results of elemental analysis were as follows.
ＨＮＯ
（ｗＨ） （ｗｔ駕） （ｗｔ＄） （ｗＨ）測
定値 ７８Ｊ ３．５ ５．７ １２．２理
論値 ７８．７８ ３．４Ｂ ５．４１ １２
．３８この分子量と元素分析との測定結果から、得られ
た白色の結晶体の分子式はＣ３４Ｈ１８０４Ｎ２で表わ
され、前述の式！で示されるクラウンエーテル化合物で
あることが判明された。HNO (wH) (wt) (wt$) (wH) Measured value 78J 3.5 5.7 12.2 Theoretical value 78.78 3.4B 5.41 12
．． 38 From the results of this molecular weight and elemental analysis, the molecular formula of the obtained white crystalline substance is represented by C34H1804N2, which is the above-mentioned formula! It turned out to be a crown ether compound shown by
また１本化合物の熱的性質として、融点が存在せず、熱
分解開始温度が５２５℃であり、極めて熱的に安定な化
合物であった。Furthermore, regarding the thermal properties of this compound, there was no melting point, and the thermal decomposition initiation temperature was 525° C., making it an extremely thermally stable compound.
更に１本化合物は合成樹脂の難燃剤として有用であり、
難燃性の効果を参考例として以下に述べる。Furthermore, this compound is useful as a flame retardant for synthetic resins,
The flame retardant effect will be described below as a reference example.
（参考例１）
実施例１で得られたクラウンエーテル化合物をポリカー
ボネート樹脂の難燃剤として添加し、難燃性を試験した
。ポリカーボネート樹脂のベレットに対しこのクラウン
エーテル化合物を第１表に示す割合で、配合し、ラボプ
ラストミルにより２８０℃で５分間混練し、プレスして
シートを作成した。これらのシートから、試験片として
縦６，５ｍｍ、横１００ ｍｍ、肉厚１．８ｍｍの試料
をそれぞれ採り、難燃性を示す酸素指数を測定し、その
結果を第１表に示した。尚、比較例として本発明のクラ
ウンエーテル化合物を配合しない試験片についても同様
に酸素指数を測定して第１表に示した。(Reference Example 1) The crown ether compound obtained in Example 1 was added as a flame retardant to polycarbonate resin, and flame retardancy was tested. This crown ether compound was blended into a pellet of polycarbonate resin in the proportions shown in Table 1, kneaded for 5 minutes at 280° C. using a laboplast mill, and pressed to form a sheet. Samples measuring 6.5 mm long, 100 mm wide, and 1.8 mm thick were taken from these sheets as test pieces, and the oxygen index, which indicates flame retardance, was measured. The results are shown in Table 1. As a comparative example, the oxygen index was similarly measured for a test piece not containing the crown ether compound of the present invention, and the results are shown in Table 1.
第 １ 表
尚、酸素指数の測定法は、Ｊ Ｉ Ｓ Ｋ７０１２に
準拠した。Table 1 Note that the method for measuring the oxygen index was based on JIS K7012.
第１表に示す如く、本発明のクラウンエーテル化合物は
ポリカーボネートの難燃剤としての有効であることが明
らかに分った。As shown in Table 1, the crown ether compounds of the present invention were clearly found to be effective as flame retardants for polycarbonates.
Claims (2)
ヒドロキシナフタレンのアルカリ金属塩とを中性極性溶
媒中で反応させ、式 I ▲数式、化学式、表等があります▼（ I ） で示されるクラウンエーテル化合物を製造することを特
徴とするクラウンエーテル化合物の製造方法。(2) 2,6-dihalogenobenzonitrile and an alkali metal salt of 2,7-dihydroxynaphthalene are reacted in a neutral polar solvent, and the reaction is shown by the formula I ▲Mathematical formula, chemical formula, table, etc.▼(I) A method for producing a crown ether compound, characterized by producing a crown ether compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9078386A JPS62246568A (en) | 1986-04-18 | 1986-04-18 | Crown ether compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9078386A JPS62246568A (en) | 1986-04-18 | 1986-04-18 | Crown ether compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62246568A true JPS62246568A (en) | 1987-10-27 |
| JPH0548231B2 JPH0548231B2 (en) | 1993-07-20 |
Family
ID=14008194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9078386A Granted JPS62246568A (en) | 1986-04-18 | 1986-04-18 | Crown ether compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62246568A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012081391A1 (en) * | 2010-12-16 | 2012-06-21 | 三菱エンジニアリングプラスチックス株式会社 | Flame-retardant polycarbonate resin composition, flame retardant for polycarbonate resin, and method for producing same. |
-
1986
- 1986-04-18 JP JP9078386A patent/JPS62246568A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012081391A1 (en) * | 2010-12-16 | 2012-06-21 | 三菱エンジニアリングプラスチックス株式会社 | Flame-retardant polycarbonate resin composition, flame retardant for polycarbonate resin, and method for producing same. |
| US9115269B2 (en) | 2010-12-16 | 2015-08-25 | Mitsubishi Engineering-Plastics Corporation | Flame retardant polycarbonate resin composition, flame retardant for polycarbonate resin, and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0548231B2 (en) | 1993-07-20 |
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