JPH0791259B2 - Method for producing phthalonitrile compound - Google Patents
Method for producing phthalonitrile compoundInfo
- Publication number
- JPH0791259B2 JPH0791259B2 JP9760289A JP9760289A JPH0791259B2 JP H0791259 B2 JPH0791259 B2 JP H0791259B2 JP 9760289 A JP9760289 A JP 9760289A JP 9760289 A JP9760289 A JP 9760289A JP H0791259 B2 JPH0791259 B2 JP H0791259B2
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- JP
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- compound
- formula
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- 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.)
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- -1 phthalonitrile compound Chemical class 0.000 title claims description 19
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KMCYRPYZMBMRAZ-UHFFFAOYSA-N 4,5-dichloro-1,4-dihydroxycyclohexa-2,5-diene-1,2-dicarbonitrile Chemical compound OC1(Cl)C=C(C#N)C(O)(C#N)C=C1Cl KMCYRPYZMBMRAZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001007 phthalocyanine dye Substances 0.000 description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- GNXDRIAMVNVFMO-UHFFFAOYSA-N 1,4-dihydroxycyclohexa-3,5-diene-1,2-dicarbonitrile Chemical compound OC1=CC(C#N)C(O)(C#N)C=C1 GNXDRIAMVNVFMO-UHFFFAOYSA-N 0.000 description 1
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 125000006350 alkyl thio alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000006351 ethylthiomethyl group Chemical group [H]C([H])([H])C([H])([H])SC([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000006533 methyl amino methyl group Chemical group [H]N(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004372 methylthioethyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])* 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 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 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 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
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 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
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はオプトエレクトロニクス材料としての光記録媒
体、光カード、レーザープリンター、近赤外線吸収フィ
ルター、保護眼鏡などに用いられる新規フタロシアニン
化合物の中間体として有用なフタロニトリル化合物の製
造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is an intermediate of a novel phthalocyanine compound used for an optical recording medium as an optoelectronic material, an optical card, a laser printer, a near-infrared absorbing filter, protective glasses and the like. The present invention relates to a method for producing a useful phthalonitrile compound.
モノアルコキシフタロニトリルは公知化合物として知ら
れており、フタロシアニン系色素の出発物質として有用
な化合物である。この化合物は1,2−ジシアノハイドロ
キノンまたは1,2−ジシアノ−4,5−ジクロロハイドロキ
ノンとハロゲン化アルキルを塩基の存在下、反応させる
ことにより得ることができる。しかしながら、副生成物
として、３位および６位に同一のアルコキシ基が置換し
た、ジアルコキシフタロニトリルも相当量得られ、目的
とするモノアルコキシフタロニトリルを高収率で得るこ
とは困難であった。Monoalkoxyphthalonitrile is known as a known compound and is a useful compound as a starting material for a phthalocyanine dye. This compound can be obtained by reacting 1,2-dicyanohydroquinone or 1,2-dicyano-4,5-dichlorohydroquinone with an alkyl halide in the presence of a base. However, a considerable amount of dialkoxyphthalonitrile in which the same alkoxy group is substituted at the 3- and 6-positions was obtained as a by-product, and it was difficult to obtain the desired monoalkoxyphthalonitrile in high yield. .
本発明の目的は、フタロシアニン系色素の出発原料とな
るモノアルコキシフタロニトリル化合物の選択的製造方
法を提供することである。An object of the present invention is to provide a method for selectively producing a monoalkoxyphthalonitrile compound which is a starting material for a phthalocyanine dye.
本発明は、反応系における反応溶媒を特定することによ
り達成されたものである。即ち本発明は一般式（Ｉ） ［式（Ｉ）中、Ｒは炭素数１〜20の未置換または置換ア
ルキル基を表わし、Ｘは水素原子またはハロゲン原子を
表わす］で示されるフタロニトリル化合物を選択的に得
る方法であり、一般式（II） ［式（II）中、Ｘは式（Ｉ）中のＸと同一の意味を表わ
す］で示される化合物と一般式（III） RY （III） ［式中Ｒは式（Ｉ）中のＲと同一の意味を表わし、Ｙは
ハロゲン原子を表わす。］で示される化合物を、ジメチ
ルホルムアミド中、塩基の存在下で反応させることによ
り高収率で該フタロニトリル化合物を得る製造方法であ
る。The present invention has been achieved by specifying the reaction solvent in the reaction system. That is, the present invention has the general formula (I) [In the formula (I), R represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, X represents a hydrogen atom or a halogen atom], which is a method for selectively obtaining a phthalonitrile compound, Formula (II) [In the formula (II), X represents the same meaning as X in the formula (I)] and a compound represented by the general formula (III) RY (III) [wherein R represents R in the formula (I)] It has the same meaning and Y represents a halogen atom. ] It is a manufacturing method which obtains this phthalonitrile compound in high yield by making the compound shown by these react in dimethylformamide in presence of a base.
式（Ｉ）、（II）および（III）中のＲの未置換または
置換アルキル基としては、例えば、メチル基、エチル
基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、
ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ
−ドデシル基、ｎ−ヘキサデシル基、iso−ブチル基、
ｔ−ブチル基、iso−アミル基、neo−ペンチル基、iso
−ヘキシル基、２−エチルヘキシル基、3,5,5−トリメ
チルヘキシル基、シクロヘキシル基などの炭素数１〜20
の直鎖、分岐または環状の炭化水素基、メトキシメチル
基、エトキシメチル基、メトキシエチル基、メトキシブ
チル基、エトキシエトキシエチル基などのアルコキシア
ルキル基、ヒドロキシエチル基などのヒドロキシアルキ
ル基、メチルアミノメチル基、ジメチルアミノエチル基
などのアルキルアミノアルキル基、メチルチオメチル
基、エチルチオメチル基、メチルチオエチル基などのア
ルキルチオアルキル基、ベンジル基、フェニルエチル
基、ナフチルメチル基、ｐ−ｔ−ブチルベンジル基など
のアラルキル基、アリル基、クロチル基、メタリル基、
３−メチル−２−ブテニル基などのアルケニル基などが
挙げられる。Examples of the unsubstituted or substituted alkyl group represented by R in formulas (I), (II) and (III) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group,
n-hexyl group, n-heptyl group, n-octyl group, n
-Dodecyl group, n-hexadecyl group, iso-butyl group,
t-butyl group, iso-amyl group, neo-pentyl group, iso
1 to 20 carbon atoms such as -hexyl group, 2-ethylhexyl group, 3,5,5-trimethylhexyl group, cyclohexyl group
Linear, branched or cyclic hydrocarbon group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, methoxybutyl group, alkoxyalkyl group such as ethoxyethoxyethyl group, hydroxyalkyl group such as hydroxyethyl group, methylaminomethyl Group, alkylaminoalkyl group such as dimethylaminoethyl group, alkylthioalkyl group such as methylthiomethyl group, ethylthiomethyl group, methylthioethyl group, benzyl group, phenylethyl group, naphthylmethyl group, pt-butylbenzyl group, etc. Aralkyl group, allyl group, crotyl group, methallyl group,
Examples thereof include an alkenyl group such as a 3-methyl-2-butenyl group.
式（Ｉ）および（II）中のＸ、および（III）中のＹの
ハロゲン原子の例としては、F,Cl,Br,Iなどが挙げられ
る。Examples of the halogen atom for X in formulas (I) and (II) and Y for (III) include F, Cl, Br, and I.
本発明においては、反応溶媒としてジメチルホルムアミ
ドを用い、塩基の存在下、一般式（II）の化合物と一般
式（III）の化合物を反応させることにより、一般式
（Ｉ）で示されるフタロニトリル化合物を製造すること
ができるものである。In the present invention, dimethylformamide is used as the reaction solvent, and the phthalonitrile compound represented by the general formula (I) is obtained by reacting the compound of the general formula (II) with the compound of the general formula (III) in the presence of a base. Can be manufactured.
本発明において用いられる塩基としては、炭酸カリウ
ム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナト
リウムなどの塩が挙げられる。Examples of the base used in the present invention include salts such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
反応で使用される化合物（III）の量は、化合物（II）
に対して、0.5〜10モル当量、好ましくは0.9〜1.2モル
当量である。塩基の使用量は化合物（II）に対して0.5
〜20モル当量であり、好ましくは、1.0〜5.0モル当量で
ある。反応温度は０℃から反応溶媒のジメチルホルムア
ミドの還流温度の範囲であり、好ましくは60℃から100
℃の範囲である。反応温度が高すぎると３位と６位の両
方に同一のアルコキシ基を有するフタロニトリルの生成
が若干促進されるので好ましくない。ジメチルホルムア
ミドの使用量は化合物（II）に対して１〜20重量倍、好
ましくは２〜５重量倍である。また、反応時間は１〜50
時間が好ましい。The amount of compound (III) used in the reaction is
To 0.5 to 10 molar equivalents, preferably 0.9 to 1.2 molar equivalents. The amount of base used is 0.5 with respect to compound (II).
To 20 molar equivalents, preferably 1.0 to 5.0 molar equivalents. The reaction temperature is in the range of 0 ° C to the reflux temperature of the reaction solvent dimethylformamide, preferably 60 ° C to 100 ° C.
It is in the range of ° C. If the reaction temperature is too high, the formation of phthalonitrile having the same alkoxy group at both the 3-position and the 6-position is slightly promoted, which is not preferable. The amount of dimethylformamide used is 1 to 20 times by weight, preferably 2 to 5 times by weight based on the compound (II). The reaction time is 1 to 50.
Time is preferred.
また化合物（II）は1,2−ジシアノ−4,5−ジクロロハイ
ドロキノンとハロゲン化アルキルを塩基の存在下、反応
させることにより得ることができる。Compound (II) can be obtained by reacting 1,2-dicyano-4,5-dichlorohydroquinone with an alkyl halide in the presence of a base.
以下、実施例により、さらに詳細に説明する。 Hereinafter, further details will be described with reference to examples.
実施例１ 下記構造式（II−１）で示される化合物22.9部と 炭酸カリウム27.6部とジメチルホルムアミド70部よりな
る混合溶液を反応容器中に入れ、60℃に加熱した後、ｎ
−オクチルブロマイド19.3部を60℃で加え、その後昇温
して80℃で80時間加熱撹拌した後、水600部中に排出し
た。これを酢酸エチルを用いて抽出し、濃縮後、カラム
精製（ヘキサン：酢酸エチル＝1:1）し、下記構造式
（Ｉ−１）で示される化合物28.0部（収率82％）を得
た。Example 1 22.9 parts of a compound represented by the following structural formula (II-1) A mixed solution consisting of 27.6 parts of potassium carbonate and 70 parts of dimethylformamide was placed in a reaction vessel and heated to 60 ° C., then n
-Octyl bromide (19.3 parts) was added at 60 ° C, the temperature was raised, the mixture was heated with stirring at 80 ° C for 80 hours, and then discharged into 600 parts of water. This was extracted with ethyl acetate, concentrated, and purified by column (hexane: ethyl acetate = 1: 1) to obtain 28.0 parts (yield: 82%) of a compound represented by the following structural formula (I-1). .
元素分析 C16H18N2O2Cl2 Ｃ Ｈ Ｎ Cl 計算値（％） 56.32 5.32 8.21 20.78 実測値（％） 56.26 5.34 8.18 20.74 赤外吸収スペクトル:3400cm-1（−OH） 2175,2150cm-1（−Ｃ≡Ｎ） MSスペクトル:MW＝341 実施例２ 構造式（II−１）で示される化合物22.9部と炭酸カリウ
ム27.6部とジメチルホルムアミド70部よりなる混合溶液
を反応容器中に入れ、60℃に加熱した後、iso−アミル
ブロマイド15.1部を60℃で加え、その後昇温して80℃で
30時間加熱撹拌した後、水600部中に排出した。これを
酢酸エチルを用いて抽出し、濃縮後、カラム精製（ヘキ
サン：酢酸エチル＝1:1）し、下記構造式（Ｉ−２）で
示される化合物23.9部（収率80％）を得た。 Elemental analysis C 16 H 18 N 2 O 2 Cl 2 C H N Cl Calculated (%) 56.32 5.32 8.21 20.78 Found (%) 56.26 5.34 8.18 20.74 IR spectrum: 3400cm -1 (-OH) 2175,2150cm - 1 (-C≡N) MS spectrum: MW = 341 Example 2 A mixed solution of 22.9 parts of the compound represented by the structural formula (II-1), 27.6 parts of potassium carbonate and 70 parts of dimethylformamide was put in a reaction vessel, After heating to 60 ° C, 15.1 parts of iso-amyl bromide was added at 60 ° C, then the temperature was raised to 80 ° C.
After heating and stirring for 30 hours, the mixture was discharged into 600 parts of water. This was extracted with ethyl acetate, concentrated, and then column purified (hexane: ethyl acetate = 1: 1) to obtain 23.9 parts (yield 80%) of a compound represented by the following structural formula (I-2). .
元素分析 C13H12N2O2Cl2 Ｃ Ｈ Ｎ Cl 計算値（％） 52.19 4.04 9.36 23.70 実測値（％） 52.15 4.08 9.31 23.65 赤外吸収スペクトル:3400cm-1（−OH） 2180,2155cm-1（−Ｃ≡Ｎ） MSスペクトル:MW＝299 実施例３ 構造式（II−１）で示される化合物22.9部と炭酸カリウ
ム27.6部とジメチルホルムアミド70部よりなる混合溶液
を反応容器中に入れ、60℃に加熱した後、２−エチルヘ
キシルブロマイド19.3部を60℃で加え、その後昇温して
80℃で30時間加熱撹拌した後、水600部中に排出した。
これを酢酸エチルを用いて抽出し、濃縮後、カラム精製
（ヘキサン：酢酸エチル＝1:1）し、下記構造式（Ｉ−
３）で示される化合物28.3部（収率83％）を得た。 Elemental analysis C 13 H 12 N 2 O 2 Cl 2 C H N Cl Calculated (%) 52.19 4.04 9.36 23.70 Found (%) 52.15 4.08 9.31 23.65 IR spectrum: 3400cm -1 (-OH) 2180,2155cm - 1 (-C≡N) MS spectrum: MW = 299 Example 3 A mixed solution of 22.9 parts of the compound represented by the structural formula (II-1), 27.6 parts of potassium carbonate and 70 parts of dimethylformamide was put into a reaction vessel, After heating to 60 ° C, 19.3 parts of 2-ethylhexyl bromide was added at 60 ° C, and then the temperature was raised.
After heating and stirring at 80 ° C. for 30 hours, the mixture was discharged into 600 parts of water.
This was extracted with ethyl acetate, concentrated, and purified by column (hexane: ethyl acetate = 1: 1) to obtain the following structural formula (I-
28.3 parts (yield 83%) of the compound represented by 3) was obtained.
元素分析 C16H18N2O2Cl2 Ｃ Ｈ Ｎ Cl 計算値（％） 56.32 5.32 8.21 20.78 実測値（％） 56.28 5.36 8.19 20.73 赤外吸収スペクトル:3400cm-1（−OH） 2175,2150cm-1（−Ｃ≡Ｎ） MSスペクトル:MW＝341 実施例４〜13 一般式（II）および一般式（III）で表わされ、表１に
示す置換基を有する化合物を用いて目的とする一般式
（Ｉ）で表されるモノアルコキシフタロニトリル化合物
を合成した。合成時の反応条件、収率を表１に示す。 Elemental analysis C 16 H 18 N 2 O 2 Cl 2 C H N Cl Calculated (%) 56.32 5.32 8.21 20.78 Found (%) 56.28 5.36 8.19 20.73 IR spectrum: 3400cm -1 (-OH) 2175,2150cm - 1 (-C≡N) MS spectrum: MW = 341 Examples 4 to 13 The compounds represented by the general formula (II) and the general formula (III) and having the substituents shown in Table 1 are used as target compounds. A monoalkoxyphthalonitrile compound represented by the formula (I) was synthesized. Table 1 shows the reaction conditions and yield at the time of synthesis.
〔発明の効果〕 本発明により、目的の一般式（Ｉ）で示されるモノアル
コキシフタロニトリル化合物を高純度かつ高収率で得る
ことができるようになった。また、このフタロニトリル
系化合物は色材の中間体としての価値も大きいものであ
る。 [Effects of the Invention] According to the present invention, it becomes possible to obtain the desired monoalkoxyphthalonitrile compound represented by the general formula (I) in high purity and high yield. Further, the phthalonitrile-based compound has great value as an intermediate for a coloring material.
Claims (1)
ルキル基を表わし、Ｘは水素原子またはハロゲン原子を
表わす］で示されるフタロニトリル化合物を製造するに
当たり、式（II） ［式（II）中、Ｘは式（Ｉ）中のＸと同一の意味を表わ
す］で示される化合物と一般式（III） RY （III） ［式中、Ｒは式（Ｉ）のＲと同一の意味を表わし、Ｙは
ハロゲン原子を表わす］で示される化合物を、ジメチル
ホルムアミド中、塩基の存在下で反応させることを特徴
とするフタロニトリル化合物の製造方法。1. A general formula (I) [In the formula (I), R represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and X represents a hydrogen atom or a halogen atom]. [In the formula (II), X represents the same meaning as X in the formula (I)] and a compound represented by the general formula (III) RY (III) [wherein, R represents R of the formula (I)] A compound having the same meaning and Y represents a halogen atom] is reacted in dimethylformamide in the presence of a base to produce a phthalonitrile compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9760289A JPH0791259B2 (en) | 1989-04-19 | 1989-04-19 | Method for producing phthalonitrile compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9760289A JPH0791259B2 (en) | 1989-04-19 | 1989-04-19 | Method for producing phthalonitrile compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02279664A JPH02279664A (en) | 1990-11-15 |
| JPH0791259B2 true JPH0791259B2 (en) | 1995-10-04 |
Family
ID=14196784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9760289A Expired - Fee Related JPH0791259B2 (en) | 1989-04-19 | 1989-04-19 | Method for producing phthalonitrile compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791259B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942504B (en) * | 2012-11-08 | 2015-05-06 | 北京理工大学 | Synthesis method of 3,6-dibromo phthalonitrile |
| CN117105817B (en) * | 2023-10-25 | 2023-12-26 | 山东佰隆医药有限公司 | Synthesis method of 2, 3-dicyanohydroquinone |
-
1989
- 1989-04-19 JP JP9760289A patent/JPH0791259B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02279664A (en) | 1990-11-15 |
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