JPH02279664A - Production of phthalonitrile compound - Google Patents
Production of phthalonitrile compoundInfo
- Publication number
- JPH02279664A JPH02279664A JP9760289A JP9760289A JPH02279664A JP H02279664 A JPH02279664 A JP H02279664A JP 9760289 A JP9760289 A JP 9760289A JP 9760289 A JP9760289 A JP 9760289A JP H02279664 A JPH02279664 A JP H02279664A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- compound
- component
- dimethylformamide
- 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 phthalonitrile compound Chemical class 0.000 title claims abstract description 18
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 4
- 150000001350 alkyl halides Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000005693 optoelectronics Effects 0.000 abstract description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound 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 abstract description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 abstract description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 abstract description 2
- 239000011736 potassium bicarbonate Substances 0.000 abstract description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 abstract description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 2
- 235000017550 sodium carbonate Nutrition 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 235000015320 potassium carbonate Nutrition 0.000 abstract 1
- 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 7
- 238000000862 absorption spectrum Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 238000001228 spectrum 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001007 phthalocyanine dye Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-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
- 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 125000000217 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
- 125000006487 butyl benzyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 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
- 238000000921 elemental analysis Methods 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
- 125000006351 ethylthiomethyl group Chemical group [H]C([H])([H])C([H])([H])SC([H])([H])* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 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
- 239000000203 mixture Substances 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
- 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 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)
Abstract
Description
【発明の詳細な説明】
【産業上の利用分野１
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 [Industrial Application Field 1] The present invention is applicable to optical recording media as optoelectronic materials, optical cards, laser printers, near-infrared absorption filters, safety glasses, etc. as intermediates for novel phthalocyanine compounds. The present invention relates to a method for producing useful phthalonitrile compounds.
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高収率で
得ることは困難であった。Monoalkoxyphthalonitrile is a known compound and is a compound useful as a starting material for phthalocyanine dyes. 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,
As a by-product, a considerable amount of dialkoxyphthalonitrile substituted with the same alkoxy group at the 3- and 6-positions was also obtained, making it difficult to obtain the desired monoalkoxyphthalonitrile in high yield.
［発明が解決しようとする課題１
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。[Problem to be Solved by the Invention 1] An object of the present invention is to provide a method for selectively producing a monoalkoxyphthalonitrile compound that 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）
Ｒ
Ｈ
［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［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 （ｍ）
［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の製造方法で
ある。The present invention was achieved by specifying the reaction solvent in the reaction system. That is, the present invention provides a phthalonitrile represented by the general formula (I) R H [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] This is a method for selectively obtaining compounds of the general formula [formula (II), where X is formula (I)
The compound represented by the general formula (III) RY (m) [wherein R represents the same meaning as R in formula (I), and Y represents a halogen atom. This is a manufacturing method for obtaining the phthalonitrile compound in high yield by reacting the compound shown in dimethylformamide in the presence of a base.
式ＣＩ）、（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−へブチル基、ｎ−オクチル基、
ｎ−ドデシル基、ｎ−ヘキサデシル基、ｉａｏ−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 unsubstituted or substituted alkyl groups for R in formulas CI), (II) and (III) include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group. group, n-hebutyl group, n-octyl group,
n-dodecyl group, n-hexadecyl group, iao-butyl group, t-butyl group, iso-amyl group, neo-pentyl group, iso-hexyl group, 2-ethylhexyl group, 3
, 5. 5- Straight chain, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms such as trimethylhexyl group and cyclohexyl group; alkoxy groups such as methoxymethyl group, ethoxymethyl group, methoxyethyl group, methoxybutyl group and ethoxyethoxyethyl group; Alkyl group, hydroxyalkyl group such as hydroxyethyl group, alkylaminoalkyl group such as methylaminomethyl group, dimethylaminoethyl group, alkylthioalkyl group such as methylthiomethyl group, ethylthiomethyl group, methylthioethyl group, benzyl group, phenyl group Ethyl group, naphthylmethyl group, p-t-
Examples include aralkyl groups such as a butylbenzyl group, and alkenyl groups such as an allyl group, a crotyl group, a methallyl group, and 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． Ｃ１． Ｂｒ．
１などが挙げられる。Examples of the halogen atoms of X in formulas (I) and (II) and Y in formula (III) include F. C1. Br.
1 etc.
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（１）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, the phthalonitrile compound represented by the general formula (1) is prepared by reacting the compound of the general formula (II) with the compound of the general formula (III) in the presence of a base using dimethylformamide as a reaction solvent. 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（ｍ）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 (m) used in the reaction is the amount of compound (II)
0.5 to 10 molar equivalents, preferably 0.9 to 10 molar equivalents to
It is 1.2 molar equivalent. The amount of base used is based on compound (II)
0.5 to 20 molar equivalents, preferably,
The molar equivalent is 1.0 to 5.0. The reaction temperature ranges from 0°C to the reflux temperature of dimethylformamide as a reaction solvent, preferably from 60°C to 100°C. If the reaction temperature is too high, the formation of phthalonitrile having the same alkoxy group at both the 3- and 6-positions is slightly accelerated, which is not preferable. The amount of dimethylformamide used is
It is 1 to 20 times by weight, preferably 2 to 5 times by weight, relative to II). Further, the reaction time is preferably 1 to 50 hours.
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 also be obtained by reacting 1,2-dicyano-4,5-dichlorohydroquinone with an alkyl halide in the presence of a base.
〔実施例］ 以下、実施例により、さらに詳細に説明する。〔Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
下記構造式（ＩＩ−１）で示される化合物２２．９部と
ＯＨ
Ｎ
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時間加熱攪拌した後、
水６００部中に排出した。これを酢酸エチルな用いて抽
出し、濃縮後、カラム精製（ヘキサン：酢酸エチル＝１
：１）Ｌ、下記構造式（Ｉ−１）で示される化合物２８
．０部（収率８２％）を得た。A mixed solution consisting of 22.9 parts of the compound represented by the following structural formula (II-1), 27.6 parts of OHN potassium carbonate, and 70 parts of dimethylformamide was placed in a reaction vessel, heated to 60°C, and then n- 19.3 parts of octyl bromide was added at 60°C, and then the temperature was raised and stirred at 80°C for 80 hours.
Discharged into 600 parts of water. This was extracted using ethyl acetate, concentrated, and then column purified (hexane:ethyl acetate = 1
:1) L, compound 28 represented by the following structural formula (I-1)
．． 0 parts (yield 82%) were obtained.
ＯＨ
元素分析 Ｃ８゜Ｈ＋ａＮｉＯ□Ｃ１ａＣＨＮ
Ｃ１
計算値（％） ５６．３２ ５．３２ ８．２１ ２
０．７８実測値（％） ５６．２６ ５．３４ ８．
１８ ２０．７４赤外吸収スペクトル： ３４００ ａ
ｍ”’ （−ＯＨ）２１７５．２１５０ｃｍ−１（−Ｃ
三Ｎ）ＭＳスペクトル： ＭＷ−３４１
寒立且ｌ
構造式（ｎ−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、
１ｓｏ−アミルブロマイド１５．１部を６０℃で加え、
その後昇温しで８０℃で３０時間加熱攪拌した後、水６
００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
）Ｌ、下記構造式（Ｉ−２）で示される化合物２３．９
部（収率８０％）を得た。OH elemental analysis C8゜H+aNiO□C1aCHN
C1 Calculated value (%) 56.32 5.32 8.21 2
0.78 Actual value (%) 56.26 5.34 8.
18 20.74 Infrared absorption spectrum: 3400 a
m"' (-OH)2175.2150cm-1(-C
3N) MS Spectrum: MW-341 A mixed solution consisting of 22.9 parts of the compound represented by structural formula (n-1), 27.6 parts of potassium carbonate, and 70 parts of dimethylformamide was placed in a reaction vessel. , after heating to 60°C,
Add 15.1 parts of 1so-amyl bromide at 60°C,
After that, the temperature was raised to 80°C for 30 hours with stirring, and then water was heated to 60°C.
It was discharged into 00 copies. This was extracted using ethyl acetate, concentrated, and then column purified (hexane: ethyl acetate = 1:1
)L, compound 23.9 represented by the following structural formula (I-2)
(yield: 80%).
した後、２−エチルヘキシルブロマイド１９．３部を６
０℃で加え、その後昇温しで８０℃で３０時間加熱攪拌
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）Ｌ／、下記構造式（Ｉ−３）で示される
化合物２８．３部（収率８３％）を得た。After that, 19.3 parts of 2-ethylhexyl bromide was added to 6
The mixture was added at 0°C, then heated and stirred at 80°C for 30 hours, and then discharged into 600 parts of water. This was extracted using ethyl acetate, and after concentration, column purification (hexane: ethyl acetate = 1:1) L/L yielded 28.3 parts of the compound represented by the following structural formula (I-3) (yield: 83%) I got it.
計算値（％） ５２．１９ ４．０４ ９．３６ ２
３．７０実測値（％） ５２．１５ ４．０８ ９．
３１ ２３．６５赤外吸収スペクトル： ３４００ ｃ
ｍ−１（−０Ｈ）２１８０、２１５５ｃｎ＋−’ （−
ＣミＮ）ＭＳスペクトル： ＭＷ−２９９
Ｘ１皿ｌ
構造式（ｎ−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℃に加熱計算値（
％） ５６．３２ ５．３２ ８．２１ ２０．７８
実測値（％） ５６．２８ ５．３６ ８．１９ ２
０．７３赤外吸収スペクトル： ３４００ ａｍ”’
（−０）１ ）２１７５．２１５０ｃｍ−１（−Ｃ＝Ｎ
）ＭＳスペクトル： ＭＷ−３４１
衷Ｗ辷二■
一般式（ＩＩ）および−数式（ｍ）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二トリル化合物を
合成した。Calculated value (%) 52.19 4.04 9.36 2
3.70 Actual value (%) 52.15 4.08 9.
31 23.65 Infrared absorption spectrum: 3400 c
m-1 (-0H) 2180, 2155cn+-' (-
Cmi N) MS spectrum: MW-299 , heating calculation value to 60℃ (
%) 56.32 5.32 8.21 20.78
Actual value (%) 56.28 5.36 8.19 2
0.73 Infrared absorption spectrum: 3400 am"'
(-0)1 )2175.2150cm-1(-C=N
) MS spectrum: MW-341 衷W辷二■ Compounds represented by the general formula (II) and -numerical formula (m) and having the substituents shown in Table 1 were used to obtain the desired general formula (
A monoalkoxyphthalonitrile compound represented by I) was synthesized.
合成時の反応条 件、 収率な表１に示す。Reaction conditions during synthesis subject, The yield is shown in Table 1.
０■
Ｎ
Ｙ
（ＩＩ［）
（以下余白）
〔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。0■ N Y (II [) (hereinafter referred to as blank space) [Effects of the Invention] According to the present invention, the target monoalkoxyphthalonitrile compound represented by general formula (I) can be obtained with high purity and high yield. became. In addition, this phthalonitrile compound has great value as an intermediate for coloring materials.
特許出願人 三井東圧化学株式会社 山本化成株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd. Yamamoto Kasei Co., Ltd.
Claims (1)
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製造す
るに当たり、式（II） ▲数式、化学式、表等があります▼（II） ［式（II）中、Ｘは式（ I ）中のＲおよび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を
特徴とするフタロニトリル化合物の製造方法。[Claims] 1. General formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In 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] In manufacturing a phthalonitrile compound represented by the formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (II) [In the formula (II), X represents the formula ( I )] and the compound represented by the general formula (III) RY(III) [wherein R represents the same meaning as R in formula (I), Y
represents a halogen atom. ] A method for producing a phthalonitrile compound, which comprises reacting a compound represented by the following in dimethylformamide in the presence of a base.
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 true JPH02279664A (en) | 1990-11-15 |
| JPH0791259B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942504A (en) * | 2012-11-08 | 2013-02-27 | 北京理工大学 | Synthesis method of 3,6-dibromo phthalonitrile |
| CN117105817A (en) * | 2023-10-25 | 2023-11-24 | 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
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942504A (en) * | 2012-11-08 | 2013-02-27 | 北京理工大学 | Synthesis method of 3,6-dibromo phthalonitrile |
| CN117105817A (en) * | 2023-10-25 | 2023-11-24 | 山东佰隆医药有限公司 | Synthesis method of 2, 3-dicyanohydroquinone |
| CN117105817B (en) * | 2023-10-25 | 2023-12-26 | 山东佰隆医药有限公司 | Synthesis method of 2, 3-dicyanohydroquinone |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791259B2 (en) | 1995-10-04 |
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