JP3681195B2 - Phthalonitrile compounds - Google Patents
Phthalonitrile compounds Download PDFInfo
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- JP3681195B2 JP3681195B2 JP09515095A JP9515095A JP3681195B2 JP 3681195 B2 JP3681195 B2 JP 3681195B2 JP 09515095 A JP09515095 A JP 09515095A JP 9515095 A JP9515095 A JP 9515095A JP 3681195 B2 JP3681195 B2 JP 3681195B2
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- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 title description 5
- -1 phthalonitrile compound Chemical class 0.000 claims description 61
- 239000000126 substance Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000005309 thioalkoxy group Chemical group 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 20
- 238000000921 elemental analysis Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSNWKQHTZXPWJS-UHFFFAOYSA-N 4-ethynyl-2,6-dimethylheptan-4-ol Chemical compound CC(C)CC(O)(C#C)CC(C)C CSNWKQHTZXPWJS-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- UZJZIZFCQFZDHP-UHFFFAOYSA-N 3-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1C#N UZJZIZFCQFZDHP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical group C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- VZWXIQHBIQLMPN-UHFFFAOYSA-N chromane Chemical compound C1=CC=C2CCCOC2=C1 VZWXIQHBIQLMPN-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000006033 1,1-dimethyl-2-propenyl group Chemical group 0.000 description 1
- 125000006037 1-ethyl-2-propenyl group Chemical group 0.000 description 1
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 1
- 125000006028 1-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000003764 2,4-dimethylpentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004714 2-methylbutylthio group Chemical group CC(CS*)CC 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- PUNRPAWKFTXZIW-UHFFFAOYSA-N 3-ethylpent-1-yn-3-ol Chemical compound CCC(O)(CC)C#C PUNRPAWKFTXZIW-UHFFFAOYSA-N 0.000 description 1
- 125000003469 3-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- DIFXCBNNWBBNCA-UHFFFAOYSA-N 4-methyl-3-propan-2-ylpent-1-yn-3-ol Chemical compound CC(C)C(O)(C#C)C(C)C DIFXCBNNWBBNCA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)(C#C)Oc1cccc(C#N)c1C#N Chemical compound CC(*)(C#C)Oc1cccc(C#N)c1C#N 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000006316 iso-butyl amino group Chemical group [H]N(*)C([H])([H])C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000005921 isopentoxy group Chemical group 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- XWCQLLDGXBLGMD-UHFFFAOYSA-M magnesium;pentane;bromide Chemical compound [Mg+2].[Br-].CCCC[CH2-] XWCQLLDGXBLGMD-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004708 n-butylthio group Chemical group C(CCC)S* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004712 n-pentylthio group Chemical group C(CCCC)S* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004888 n-propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【産業上の利用分野】
本発明は、新規のフタロニトリル系化合物に関するものである。本発明のフタロニトリル系化合物は、医薬、農薬、各種工業薬品の中間体として有用であり、例えば、光ディスク用記録材料、情報記録、表示センサー、保護眼鏡等のオプトエレクトロニクス材料として用いられるフタロシアニン化合物の中間体として、極めて有用である。
【０００２】
【従来の技術】
フタロニトリルの選択的位置に、各種置換基を有するジヒドロピラン環が縮環したジヒドロベンゾピラン系のフタロニトリル化合物は、これまで知られていない。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、各種のオプトエレクトロニクス材料として用いられるフタロシアニン化合物の製造中間体として、極めて有用な新規なフタロニトリル系化合物を提供することである。
【０００４】
【課題を解決するための手段】
本発明者らは、前項の課題を解決すべく鋭意検討した結果、本発明を完成するに至った。即ち、本発明は、一般式（１）（化２）で表されるフタロニトリル系化合物に関するものである。
【０００５】
【化２】
一般式（１）の化合物は、種々の方法で製造できるが、代表的には、下記（化３）の合成経路により製造できる。
【０００６】
【化３】
【０００７】
即ち、（ａ）で表されるアセチレンアルコールを水素化ナトリウムと反応して得られるナトリウムアルコキシドと、（ｂ）で表される3-ニトロフタロニトリルとを、N,N-ジメチルホルムアミド等の非プロトン性極性溶媒中で、０〜１００℃で反応して（ｃ）で表される化合物とし、その後さらに、公知のクライゼン転移反応の条件、即ち、高沸点溶媒中、１００〜２５０℃で反応して（ｄ）で表される化合物とする。更に、（ｄ）で表される化合物より、例えば、
G.P.Ellis and I.M.Lockhart,「CHROMANS AND TOCOPHEROLS」 (The Chemistry of heterocyclic compounds; Vol.36) An Interscience publication (1981) やA.R.Katritzky and A.J.Boulton,「Avances in HETEROCYCLIC CHEMISTRY 」Vol.18,Academic Press(1975) 記載の方法で、各種置換基を導入する反応を行うことにより一般式（１）の化合物を製造することができる。
【０００８】
一般式（１）において、Ｒ1 及びＲ2 で示される結合して環を形成していてもよい炭素数１〜１５のアルキル基の具体例としては、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、iso-ペンチル基、neo-ペンチル基、2-メチルブチル基、n-ヘキシル基、cyclo-ヘキシル基、2-エチルブチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基、2,3-ジメチルブチル基、n-ヘプチル基、2-メチルヘキシル基、3-メチルヘキシル基、4-メチルヘキシル基、5-メチルヘキシル基、2,4-ジメチルペンチル基、n-オクチル基、2-エチルヘキシル基、2,5-ジメチルヘキシル基、2,5,5-トリメチルヘキシル基、2,4-ジメチルヘキシル基、2,2,4-トリメチルペンチル基、n-ノニル基、n-デシル基、4-エチルオクチル基、4-エチル-4,5- メチルヘキシル基、n-ウンデシル基、n-ドデシル基、1,3,5,7-テトラメチルオクチル基、4-ブチルオクチル基、6,6-ジエチルオクチル基、n-トリデシル基、6-メチル-4- ブチルオクチル基、n-テトラデシル基、n-ペンタデシル基、3,5-ジメチルヘプチル基、2,6-ジメチルヘプチル基、2,4-ジメチルヘプチル基、2,2,5,5-テトラメチルヘキシル基、1-cyclo-ペンチル-2,2- ジメチルプロピル基、1-cyclo-ヘキシル-2,2- ジメチルプロピル基等が挙げられ、特に好ましくは、炭素数３〜１０の直鎖状あるいは分岐状のアルキル基である。
これらのアセチレンアルコールの一部は市販されており、容易に入手できる。
【０００９】
一般式（１）において、Ｒ3 及びＲ4 で示されるハロゲン原子の具体例としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられ、炭素数１〜５のアルキル基の具体例としては、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基、iso-ブチル基、sec-ブチル基、t-ブチル基、n-ペンチル基、iso-ペンチル基、neo-ペンチル基、2-メチルブチル基等が挙げられ、炭素数１〜５のアルコキシ基の具体例としては、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、iso-ブトキシ基、sec-ブトキシ基、t-ブトキシ基、n-ペントキシ基、iso-ペントキシ基、neo-ペントキシ基、2-メチルブトキシ基等が挙げられ、炭素数１〜５のチオアルコキシ基の具体例としては、メチルチオ基、エチルチオ基、n-プロピルチオ基、iso-プロピルチオ基、n-ブチルチオ基、iso-ブチルチオ基、sec-ブチルチオ基、t-ブチルチオ基、n-ペンチルチオ基、iso-ペンチルチオ基、neo-ペンチルチオ基、2-メチルブチルチオ基等が挙げられ、炭素数１〜８のアルキルアミノ基の具体例としては、メチルアミノ基、エチルアミノ基、n-プロピルアミノ基、iso-プロピルアミノ基、n-ブチルアミノ基、iso-ブチルアミノ基、sec-ブチルアミノ基、t-ブチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジn-プロピルアミノ基、ジiso-プロピルアミノ基、ジ（n-ブチル）アミノ基、ジ（iso-ブチル）アミノ基、ジ（sec-ブチル）アミノ基、ジ（t-ブチル）アミノ基等が挙げられ、炭素数２〜５のアルケニル基の具体例としては、エテニル基、プロペニル基、2-プロペニル基、1-メチルプロペニル基、1-メチル-2- プロペニル基、1-エチルプロペニル基、1-エチル-2- プロペニル基、1,1-ジメチル-2- プロペニル基、ブテニル基、2-ブテニル基、1-メチル-2- ブテニル基、1-メチルブテニル基、2-メチル-2- ブテニル基、2-メチルブテニル基、3-メチル-2- ブテニル基、3-メチルブテニル基等が挙げられる。
【００１０】
【実施例】
以下、実施例により本発明を具体的に説明するが、勿論、本発明はこれらの実施例によって限定されるものではない。
実施例１
窒素気流下、０〜５℃に冷却したＤＭＦ１１４部に、５５％水素化ナトリウム９．６部を加え、１時間攪拌した。同温度で、３−イソブチル−５−メチル−１−ヘキシン−３−オール３７．７部を滴下し、２時間攪拌し、アルコシド溶液を調製した。
３−ニトロフタロニトリル３４．６部をＤＭＦ１１４部に溶解させた後、０〜５℃に冷却し、先に調製したアルコキシド溶液を、内温を０〜５℃に保つようにして、２時間を要して滴下した。滴下後、同温度で４時間攪拌し、得られた反応溶液を２％塩酸水に排出した。析出物を濾過、乾燥した後、トルエン再結晶により精製し、下記式（Ｃ−１）（化４）で表される化合物４４．２部（収率７５％）を得た。
【００１１】
【化４】
【００１２】
【化５】
【００１３】
【化６】
7.40(d,1H),7.20(d,1H),2.90(t,2H), 1.40〜2.00(m,8H),1.00(d,12H)
ＩＲ( KBr ) cm-1 ２２３０
Ｍａｓｓ ｍ／ｚ ２９６
【００１４】
実施例２
実施例１において、３−イソブチル−５−メチル−１−ヘキシン−３−オールの代わりに、３−イソプロピル−４−メチル−１−ペンチン−３−オールを用いる以外は、実施例１と同様にして製造した下記式（ｄ−２）（化７）で表される化合物１５部と１５０部の四塩化炭素溶液中に、２５〜３０℃の温度で、臭素１８部を滴下し、同温度で１時間攪拌した。有機層を飽和炭酸水素ナトリウム水溶液及び水で洗浄後、四塩化炭素を留去し、トルエン再結晶により精製し、下記式（１−２）（化７）の化合物２３．０部（収率９５％）を得た。
【００１５】
【化７】
7.79(d,1H),7.41(d,1H),5.55(d,1H),4.61(d,1H),1.80〜2.20(m,2H),
0.97(d,12H)
ＩＲ( KBr ) cm-1 ２２３０
Ｍａｓｓ ｍ／ｚ ２６６
【００１６】
実施例３
実施例１において、３−イソブチル−５−メチル−１−ヘキシン−３−オールの代わりに、３−エチル−１−ペンチン−３−オールを用いる以外は、実施例１と同様にして製造した下記式（１−３）（化８）で表される化合物１０部、N-ブロムコハク酸イミド９部、過酸化ベンゾイル０．９部を１００部の四塩化炭素溶液中で４時間還流攪拌した。有機層を飽和炭酸水素ナトリウム水溶液及び水で洗浄後、四塩化炭素を溜去し、トルエン再結晶により精製し、下記式（１−４）（化９）で表される化合物１２部（収率９０％）を得た。
【００１７】
【化８】
7.40(d,1H),7.20(d,1H),2.90(t,2H), 1.40〜2.00(m,6H),1.00(t,6H)
ＩＲ( KBr ) cm-1 ２２３０
Ｍａｓｓ ｍ／ｚ ２４０
【００１８】
【化９】
7.80(d,1H),7.30(d,1H),5.30(m,1H),2.51(m,2H),2.00〜1.50(m,4H),
1.00(dd,6H)
ＩＲ( KBr ) cm-1 ２２３０
Ｍａｓｓ ｍ／ｚ ２４０
【００１９】
実施例４
実施例３において製造した式（１−４）で表される化合物７部、トリ-n- ブチルチンアリル１４．５部を、７０部のトルエン溶液中で、ＵＶランプを照射しながら５時間還流攪拌した。トルエンを溜去し、ヘキサン再結晶により精製し、下記構造（１−５）（化１０）の化合物５．４部（収率８８％）を得た。
【００２０】
【化１０】
7.40(d,1H),7.20(d,1H),6.00(m,1H),5.21(m,2H),3.20(m,1H),
1.80 〜2.40(m,6H),1.00(t,6H)
ＩＲ( KBr ) cm-1 ２２３０
Ｍａｓｓ ｍ／ｚ ２８０
【００２１】
実施例５
実施例１において、３−イソブチル−５−メチル−１−ヘキシン−３−オールの代わりに、１−エチニル−１−シクロヘキサノールを用いる以外は、実施例１と同様にして製造した下記式（ｄ−３）（化１１）で表される化合物２５部、ナトリウムエトキシド７．５部を１５０部のＤＭＦ溶液中、１００℃の温度で８時間加熱攪拌した。反応液を水７５０部に排出し、析出物を濾過、乾燥後、トルエンで再結晶精製し、下記構造（１−６）（化１１）で表される化合物２１．８部（収率７８％）を得た。
【００２２】
【化１１】
7.31(d,1H),7.26(d,1H),3.82(q,2H),3.20(t,1H),1.40〜2.20(m,12H),
1.00(t,3H)
ＩＲ( KBr ) cm-1 ２２３０
Ｍａｓｓ ｍ／ｚ ２８０
【００２３】
実施例６
実施例２において製造した構造式（１−２）で表される化合物１０．７部を９５部のＴＨＦ溶液中、０〜−１０℃に冷却し、ｎ- ペンチルマグネシウムブロミド（１mol/l ＴＨＦSoln）５４部を滴下し、同温度で８時間攪拌した。反応液を５００部の氷水に注いだ後、ジエチルエーテル３００部で抽出し、水洗を行なった。ジエチルエーテルを留去し、得られた粗生物をカラムクロマトグラフィーにより分離精製し、下記構造（１−７）（化１２）で表される化合物６．４部（収率６２％）を得た。
【００２４】
【化１２】
7.40(d,1H),7.20(d,1H),3.20(m,1H), 0.95〜2.40(m,37H)6
ＩＲ( KBr ) cm-1 ２２３０
Ｍａｓｓ ｍ／ｚ ４０９
【００２５】
実施例７〜１９
実施例１〜６と同様にして、第１表（表１、２）に示す一般式（１）で表される各種フタロニトリル系化合物を得た。各フタロニトリル系化合物の構造式、元素分析結果並びにＭａｓｓスペクトルの結果を第１表に示した。
【００２６】
【表１】
【表２】
【発明の効果】
本発明は、フタロニトリルの選択的位置に、各種置換基を有するジヒドロピラン環が縮環した新規なジヒドロベンゾピラン系のフタロニトリル化合物を提供するものである。これらのフタロニトリル系化合物は、光ディスク用記録材料、情報記録、表示センサー、保護眼鏡等のオプトエレクトロニクス材料として用いられるフタロシアニン化合物の中間体として非常に価値が高い。[0001]
[Industrial application fields]
The present invention relates to a novel phthalonitrile compound. The phthalonitrile compound of the present invention is useful as an intermediate for pharmaceuticals, agricultural chemicals, and various industrial chemicals. For example, a phthalocyanine compound used as an optoelectronic material such as a recording material for optical disks, information recording, a display sensor, and protective glasses. It is extremely useful as an intermediate.
[0002]
[Prior art]
A dihydrobenzopyran-based phthalonitrile compound in which a dihydropyran ring having various substituents is condensed at a selective position of phthalonitrile has not been known so far.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel phthalonitrile compound that is extremely useful as an intermediate for producing a phthalocyanine compound used as various optoelectronic materials.
[0004]
[Means for Solving the Problems]
The inventors of the present invention have intensively studied to solve the problem described in the preceding paragraph, and as a result, have completed the present invention. That is, the present invention relates to a phthalonitrile compound represented by the general formula (1) (Chemical Formula 2).
[0005]
[Chemical formula 2]
Although the compound of General formula (1) can be manufactured by various methods, it can typically be manufactured by the synthetic route of the following (Chemical Formula 3).
[0006]
[Chemical 3]
[0007]
That is, a sodium alkoxide obtained by reacting acetylene alcohol represented by (a) with sodium hydride and 3-nitrophthalonitrile represented by (b) are mixed with an aprotic compound such as N, N-dimethylformamide. In a polar solvent to form a compound represented by (c), and then further reaction under known Claisen rearrangement reaction conditions, that is, in a high boiling point solvent at 100 to 250 ° C. The compound represented by (d) is used. Further, from the compound represented by (d), for example,
GPEllis and IMLockhart, `` CHROMANS AND TOCOPHEROLS '' (The Chemistry of cyclic compounds; Vol.36) An Interscience publication (1981) and ARKatritzky and AJBoulton, `` Avances in HETEROCYCLIC CHEMISTRY '' Vol.18, Academic Press (1975) The compound of the general formula (1) can be produced by carrying out a reaction for introducing various substituents.
[0008]
In the general formula (1), specific examples of the alkyl group having 1 to 15 carbon atoms that may be bonded to form a ring represented by R 1 and R 2 include a methyl group, an ethyl group, and an n-propyl group. , Iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 2-methylbutyl group, n-hexyl group , Cyclo-hexyl group, 2-ethylbutyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3- Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylhexyl Group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-nonyl group, n-decyl group, 4- Tyloctyl group, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl Group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group 2,2,5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group and the like, particularly preferably It is a linear or branched alkyl group having 3 to 10 carbon atoms.
Some of these acetylene alcohols are commercially available and can be easily obtained.
[0009]
In the general formula (1), specific examples of the halogen atom represented by R 3 and R 4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and specific examples of the alkyl group having 1 to 5 carbon atoms. Is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl, neo- Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group. Group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, 2-methylbutoxy group and the like. Specific examples of the thioalkoxy group having 1 to 5 carbon atoms Is methylthio, ethylthio, n-propylthio, iso- Propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 2-methylbutylthio group, etc. Specific examples of the alkylamino group of formulas 1 to 8 include methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, n-butylamino group, iso-butylamino group, sec-butylamino. Group, t-butylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diiso-propylamino group, di (n-butyl) amino group, di (iso-butyl) amino group, di (sec -Butyl) amino group, di (t-butyl) amino group and the like. Specific examples of the alkenyl group having 2 to 5 carbon atoms include ethenyl group, propenyl group, 2-propenyl group, 1-methylpropenyl group, 1-methyl-2-propyl Lopenyl group, 1-ethylpropenyl group, 1-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, butenyl group, 2-butenyl group, 1-methyl-2-butenyl group, 1-methylbutenyl group 2-methyl-2-butenyl group, 2-methylbutenyl group, 3-methyl-2-butenyl group, 3-methylbutenyl group and the like.
[0010]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but it is needless to say that the present invention is not limited to these examples.
Example 1
Under a nitrogen stream, 9.6 parts of 55% sodium hydride was added to 114 parts of DMF cooled to 0 to 5 ° C. and stirred for 1 hour. At the same temperature, 37.7 parts of 3-isobutyl-5-methyl-1-hexyn-3-ol was added dropwise and stirred for 2 hours to prepare an alcoholoside solution.
After 34.6 parts of 3-nitrophthalonitrile was dissolved in 114 parts of DMF, the mixture was cooled to 0 to 5 ° C., and the alkoxide solution prepared above was allowed to remain at 0 to 5 ° C. for 2 hours. In short, it was dripped. After dropping, the mixture was stirred at the same temperature for 4 hours, and the resulting reaction solution was discharged into 2% aqueous hydrochloric acid. The precipitate was filtered and dried, and then purified by toluene recrystallization to obtain 44.2 parts (yield 75%) of a compound represented by the following formula (C-1) (Chemical formula 4).
[0011]
[Formula 4]
[0012]
[Chemical formula 5]
[0013]
[Chemical 6]
7.40 (d, 1H), 7.20 (d, 1H), 2.90 (t, 2H), 1.40 to 2.00 (m, 8H), 1.00 (d, 12H)
IR (KBr) cm -1 2230
Mass m / z 296
[0014]
Example 2
In Example 1, the same procedure as in Example 1 was used except that 3-isopropyl-4-methyl-1-pentyn-3-ol was used instead of 3-isobutyl-5-methyl-1-hexyn-3-ol. 18 parts of bromine are dropped at a temperature of 25 to 30 ° C. in 15 parts of a compound represented by the following formula (d-2) (Chemical Formula 7) and 150 parts of a carbon tetrachloride solution prepared at the same temperature. Stir for 1 hour. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and water, and then carbon tetrachloride was distilled off and purified by recrystallization with toluene to obtain 23.0 parts of a compound of the following formula (1-2) (Chemical Formula 7) (yield 95 %).
[0015]
[Chemical 7]
7.79 (d, 1H), 7.41 (d, 1H), 5.55 (d, 1H), 4.61 (d, 1H), 1.80-2.20 (m, 2H),
0.97 (d, 12H)
IR (KBr) cm -1 2230
Mass m / z 266
[0016]
Example 3
In Example 1, the following production was carried out in the same manner as in Example 1 except that 3-ethyl-1-pentyn-3-ol was used instead of 3-isobutyl-5-methyl-1-hexyn-3-ol. 10 parts of the compound represented by the formula (1-3) (Chemical Formula 8), 9 parts of N-bromosuccinimide, and 0.9 part of benzoyl peroxide were stirred under reflux in 100 parts of a carbon tetrachloride solution for 4 hours. The organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and water, and then carbon tetrachloride was distilled off and purified by toluene recrystallization, and 12 parts of a compound represented by the following formula (1-4) (Chemical formula 9) (yield) 90%).
[0017]
[Chemical 8]
7.40 (d, 1H), 7.20 (d, 1H), 2.90 (t, 2H), 1.40 to 2.00 (m, 6H), 1.00 (t, 6H)
IR (KBr) cm -1 2230
Mass m / z 240
[0018]
[Chemical 9]
7.80 (d, 1H), 7.30 (d, 1H), 5.30 (m, 1H), 2.51 (m, 2H), 2.00 to 1.50 (m, 4H),
1.00 (dd, 6H)
IR (KBr) cm -1 2230
Mass m / z 240
[0019]
Example 4
7 parts of the compound represented by the formula (1-4) produced in Example 3 and 14.5 parts of tri-n-butyltin allyl were refluxed in 70 parts of a toluene solution for 5 hours while irradiating with a UV lamp. Stir. Toluene was distilled off and purified by hexane recrystallization to obtain 5.4 parts (yield 88%) of the compound of the following structure (1-5) (Chemical Formula 10).
[0020]
[Chemical Formula 10]
7.40 (d, 1H), 7.20 (d, 1H), 6.00 (m, 1H), 5.21 (m, 2H), 3.20 (m, 1H),
1.80 to 2.40 (m, 6H), 1.00 (t, 6H)
IR (KBr) cm -1 2230
Mass m / z 280
[0021]
Example 5
In Example 1, the following formula (d) produced in the same manner as in Example 1 except that 1-ethynyl-1-cyclohexanol was used instead of 3-isobutyl-5-methyl-1-hexyn-3-ol -3) 25 parts of the compound represented by (Chemical Formula 11) and 7.5 parts of sodium ethoxide were heated and stirred at 150 ° C. for 8 hours in 150 parts of DMF solution. The reaction solution was discharged into 750 parts of water, and the precipitate was filtered, dried and then recrystallized and purified with toluene to give 21.8 parts of a compound represented by the following structure (1-6) (Chem. 11) (yield 78%). )
[0022]
Embedded image
7.31 (d, 1H), 7.26 (d, 1H), 3.82 (q, 2H), 3.20 (t, 1H), 1.40 to 2.20 (m, 12H),
1.00 (t, 3H)
IR (KBr) cm -1 2230
Mass m / z 280
[0023]
Example 6
10.7 parts of the compound represented by the structural formula (1-2) produced in Example 2 was cooled to 0 to −10 ° C. in 95 parts of a THF solution, and n-pentylmagnesium bromide (1 mol / l THFSoln) was cooled. 54 parts were added dropwise and stirred at the same temperature for 8 hours. The reaction solution was poured into 500 parts of ice water, extracted with 300 parts of diethyl ether, and washed with water. Diethyl ether was distilled off, and the resulting crude product was separated and purified by column chromatography to obtain 6.4 parts (yield 62%) of a compound represented by the following structure (1-7) (Chemical Formula 12). .
[0024]
Embedded image
7.40 (d, 1H), 7.20 (d, 1H), 3.20 (m, 1H), 0.95 to 2.40 (m, 37H) 6
IR (KBr) cm -1 2230
Mass m / z 409
[0025]
Examples 7-19
In the same manner as in Examples 1 to 6, various phthalonitrile compounds represented by the general formula (1) shown in Table 1 (Tables 1 and 2) were obtained. Table 1 shows the structural formula, elemental analysis results, and mass spectrum results of each phthalonitrile compound.
[0026]
[Table 1]
[Table 2]
【The invention's effect】
The present invention provides a novel dihydrobenzopyran-based phthalonitrile compound in which a dihydropyran ring having various substituents is condensed at a selective position of phthalonitrile. These phthalonitrile compounds are very valuable as intermediates for phthalocyanine compounds used as optoelectronic materials such as optical disk recording materials, information recording, display sensors, and protective glasses.
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