JPS6043382B2 - 4'-azidobenzal-2-methoxyacetophenone and its production method - Google Patents
4'-azidobenzal-2-methoxyacetophenone and its production methodInfo
- Publication number
- JPS6043382B2 JPS6043382B2 JP58069450A JP6945083A JPS6043382B2 JP S6043382 B2 JPS6043382 B2 JP S6043382B2 JP 58069450 A JP58069450 A JP 58069450A JP 6945083 A JP6945083 A JP 6945083A JP S6043382 B2 JPS6043382 B2 JP S6043382B2
- Authority
- JP
- Japan
- Prior art keywords
- methoxyacetophenone
- compound
- photosensitive
- azinobenza
- azidobenzal
- 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.)
- Expired
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は
式Ｎｏ Ｈ却Ｈ』 表
わされる４’−アジノベンザルー２−メトキシアセトフ
ェノン及びその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to 4'-azinobenza-2-methoxyacetophenone represented by the formula No H-H and a method for producing the same.
電子工業などの精密分野においては、感光性組成物の品
質に対する要望がきびしく粘度などの経口変化はしばし
ば半導体の製造工程等において、トラブルを起こすもと
となる。In precision fields such as the electronics industry, there are strict requirements for the quality of photosensitive compositions, and oral changes such as viscosity often cause problems in semiconductor manufacturing processes and the like.
本発明は、ネガ型の感光性化合物として溶剤への溶解性
にすぐれ、感光性高分子と組み合わせた組成物において
経口の粘度変化が小さい新規な化合物を提供するもので
ある。The present invention provides a novel compound that has excellent solubility in solvents as a negative photosensitive compound and exhibits small changes in oral viscosity when used in a composition in combination with a photosensitive polymer.
写真工業、印刷工業、電子工業等の種々の用途に感光性
化合物を適用する場合、溶剤への溶解性は大きい方が好
ましい。When applying photosensitive compounds to various uses such as the photographic industry, the printing industry, and the electronic industry, it is preferable that the compound has a high solubility in a solvent.
４’−アジノベンザルー４−メトキシアセトフェノンは
、特公昭５３−３４９０訝公報に示されているが、４’
−アジノベンザルーアセトフエノンの４の位置にメトキ
シ基が置換した分子の構造が直線的なためと思われるが
、３の位置あるいは２の位置にメトキシが置換した化合
物に比べて溶解性が小さい。4'-Azinobenzaru-4-methoxyacetophenone is disclosed in Japanese Patent Publication No. 3490/1983, but 4'
-Azinobenzaruacetophenone This is probably due to the linear structure of the molecule with a methoxy group substituted at the 4 position, but it has lower solubility than compounds with a methoxy group substituted at the 3 or 2 position. .
本発明者らは、使用するメトキシ基の置換基の・位置を
従来の置換基の位置と変更した化合物を見出したが、こ
の化合物は溶剤への溶解性を改良するものであつた。The present inventors have discovered a compound in which the position of the substituent of the methoxy group used is changed from the conventional position of the substituent, and this compound has improved solubility in solvents.
本発明は
で表わされる４″−アジノベンザルー２−メトキシアセ
トフェノン及びｐ−アジドベンズルアルデヒドと２−メ
トキシアセトフェノンとをアルカリ性化合物を触媒とし
て反応させる４″−アジノベンザルー２−メトキシアセ
トフェノンの製造法に関する。The present invention relates to a method for producing 4"-azinobenza-2-methoxyacetophenone represented by 4"-azinobenzaldehyde and 2-methoxyacetophenone in which p-azidobenzraldehyde and 2-methoxyacetophenone are reacted using an alkaline compound as a catalyst.
ｐ−アジドベンズルアルデヒドと２−メトキシアセトフ
ェノンとは同モルで反応されアルカリ性化合物としては
、水酸化ナトリウム、水酸化カリウムなどが使用できる
。p-azidobenzraldehyde and 2-methoxyacetophenone are reacted in the same molar ratio, and sodium hydroxide, potassium hydroxide, etc. can be used as the alkaline compound.
合成に使用するための溶媒としては、アルカリ性化合物
を溶解できるものが使用でき、たとえば水、メタノール
、エタノール等のアルコール類などが使用できる。合成
温度は、特に制限はないが生成物の安定性及び反応速度
から、０〜４０℃が好ましい。As the solvent for use in the synthesis, those capable of dissolving alkaline compounds can be used, such as water, alcohols such as methanol, and ethanol, and the like. The synthesis temperature is not particularly limited, but from the viewpoint of product stability and reaction rate, it is preferably 0 to 40°C.
合成は、４″−アジノベンザルー２−メトキシアセトフ
ェノンが感光性化合物であるので、黄色光下で行なうこ
とが好ましい。本発明になる化合物は、この化合物によ
り光化学的に硬化Ｃ１アルカリ水溶液に不溶液に不溶化
し得るアルカリ水溶液可溶性高分子、溶剤等と共に感光
性組成物とされる。Since 4''-azinobenza-2-methoxyacetophenone is a photosensitive compound, it is preferable to carry out the synthesis under yellow light.The compound of the present invention is photochemically cured by this compound and made insoluble in an aqueous C1 alkali solution. A photosensitive composition is prepared together with a polymer soluble in an alkaline aqueous solution, a solvent, and the like.
この高分子の例としては、水酸基またはカルボキシル基
を有する高分子であり、ノボラック樹脂、ポリヒドロキ
シスチレン樹脂、アクリル酸またはメタアクリル酸の重
合体などが用いられる。感光性組成物として使用する場
合の溶剤は、アセトン、メチルエチルケトン、メチルイ
ソブチルケトン、シクロヘキサノンなどのケトン系溶剤
、メチルセロソルブ、エチルセロソルブ、エチルセロソ
ルブ、メチルセロソルブアセテート、エチルセロソルブ
アセテート等のセロソルブ系溶剤、酢酸エチル、酢酸ブ
チル、酢酸イソアミル等のエステル系などを使用するこ
とができる。Examples of this polymer include a polymer having a hydroxyl group or a carboxyl group, such as a novolac resin, a polyhydroxystyrene resin, a polymer of acrylic acid or methacrylic acid, and the like. Solvents used in the photosensitive composition include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate, and acetic acid. Ester systems such as ethyl, butyl acetate, and isoamyl acetate can be used.
各溶剤を単独で用いても良く、２種以上の混合系で用い
てもさしつかえない。本発明になる４″−アジノベンザ
ルー２−メトキシアセトフェノンを含有する感光性組成
物は、４′−アジノベンザルー３−メトキシアセトフェ
ノン、４″−アジノベンザルー４−メトキシアセトフェ
ノン等を用いた感光性組成物に比べて経日の粘度性変化
が小さく好ましいものである。Each solvent may be used alone or in a mixture of two or more. The photosensitive composition containing 4''-azinobenzale-2-methoxyacetophenone according to the present invention has a longer shelf life than photosensitive compositions containing 4'-azinobenzale-3-methoxyacetophenone, 4''-azinobenzale-4-methoxyacetophenone, etc. The change in viscosity during the day is small, which is preferable.
本発明の実施例を説明する。Examples of the present invention will be described.
実施例１
５００ｍｔのフラスコに、２−メトキシアセトフェノン
（アルドリツチ製：純度９９％）１５ｇ，．ｐ−ア“ジ
ドベンズルアルデヒド（関東化学製）１５ｇ１１０％水
酸化ナトリウム５０ｇおよびメタノール５０ｇを入れて
、黄色光下で２５℃の温度で２橋間かくはんした。Example 1 In a 500 mt flask, 15 g of 2-methoxyacetophenone (manufactured by Aldrich, purity 99%) was added. 15 g of p-azidobenzuraldehyde (manufactured by Kanto Kagaku), 50 g of 110% sodium hydroxide, and 50 g of methanol were added and stirred for 2 hours at a temperature of 25° C. under yellow light.
反応終了後、析出した結晶をろ過により採取した。次に
水で洗浄を行ない乾燥し、エタノールから再結晶した。
２−メトキシアセトフェノンの純度は９９％であり他の
位置に置換した材料はほとんど含まれない。After the reaction was completed, the precipitated crystals were collected by filtration. Next, it was washed with water, dried, and recrystallized from ethanol.
The purity of 2-methoxyacetophenone is 99% and contains almost no materials substituted at other positions.
また、アルカリ性水溶液下における合成において２−メ
トキシアセトフェノンのメトキシ基の位置は変化しない
といえる。Furthermore, it can be said that the position of the methoxy group of 2-methoxyacetophenone does not change during synthesis under an alkaline aqueous solution.
４″−アジノベンザルー２−メトキシアセトフェノンを
以下に示す分析により確認した。4''-azinobenza-2-methoxyacetophenone was confirmed by the analysis shown below.
（４）質量分析（２００よＣ−５０１１−■）ｍ／ｅ＝
２７９第１図にスペクトルを示す。(4) Mass spectrometry (200yoC-5011-■) m/e=
279 Figure 1 shows the spectrum.
（Ｂ）ＩＲスペクトル 第２図にスペクトル（ＫＢｒ法）を示す。(B) IR spectrum Figure 2 shows the spectrum (KBr method).
２１０００−１にアジド基（−Ｎ３）の強い吸収が認め
られた。Strong absorption of azide group (-N3) was observed in 21000-1.
（Ｃ）ＮＭＲスペクトルを示す。(C) Shows the NMR spectrum.
合わせてメトキシの位置が３のスペクトル（第４図）と
４のスペクトル（第５図）も示す。第３図から、−０Ｃ
Ｈ３と〈●〉が確認された。Also shown are spectra with methoxy at position 3 (Fig. 4) and 4 (Fig. 5). From Figure 3, -0C
H3 and <●> were confirmed.
比較例てある第４図、第５図と比較して２−メトキシ基
の存在が確認される。The presence of a 2-methoxy group is confirmed by comparison with FIGS. 4 and 5, which are comparative examples.
６．８ｐｐｍから８．１ｐｐｍのスペクトルが、芳香核
のメトキシの置換基の位置によつて相違している。The spectra from 6.8 ppm to 8.1 ppm differ depending on the position of the methoxy substituent on the aromatic nucleus.
（Ｄ）結晶色 黄色 （Ｅ）紫外線吸収スペクトルの吸収極大 ３３０ｎｍ（エタノール溶媒）。(D) Crystal color yellow (E) Absorption maximum of ultraviolet absorption spectrum 330 nm (ethanol solvent).
（Ｆ）融点
９００Ｃ
実施例１で合成した４″−アジノベンザルー２−メトキ
シアセトフェノンの溶解性を類似化合物の溶解性と比較
した。(F) Melting point: 900C The solubility of 4″-azinobenza-2-methoxyacetophenone synthesized in Example 1 was compared with the solubility of similar compounds.
各溶剤に対して４″−アジノベンザルー４−メトキシア
セトフェノンの溶解量を１として比較した。The amount of 4''-azinobenza-4-methoxyacetophenone dissolved in each solvent was assumed to be 1 for comparison.
実施例１で合成した４″−アジノベンザルー２−メトキ
シアセトフェノンの経日の粘度変化比較を行なつた。Changes in viscosity over time of 4''-azinobenza-2-methoxyacetophenone synthesized in Example 1 were compared.
粘度変化の測定条件：シクロヘキサノン２５重量部、ポ
リ（ｐ−ビニルフェノール）５重量部、感光性化合物１
重量部からなる組成物を５００ｒ１ｍ以下の光をカット
した容器の中に保存し、４０℃に１か月放置し、２０′
Ｃに１か月間放置した組成物との粘度変化を比較した。Measurement conditions for viscosity change: 25 parts by weight of cyclohexanone, 5 parts by weight of poly(p-vinylphenol), 1 part by weight of photosensitive compound
The composition consisting of parts by weight was stored in a container that blocked light of 500 r1 m or less, left at 40°C for 1 month, and heated to 20'
The viscosity change was compared with that of the composition left in C for one month.
本発明になる４″−アジノベンザルー２−メトキシアセ
トフェノンは、従来のネガ型のアジド化合物に比べ、溶
剤に対する溶解性が改良され、感光性組成物とした場合
に経日の粘度変化か従来の組成物の１／２以下であるこ
とが示される。The 4''-azinobenza-2-methoxyacetophenone of the present invention has improved solubility in solvents compared to conventional negative-type azide compounds, and when used as a photosensitive composition, there is no change in viscosity over time compared to conventional compositions. It is shown that it is 1/2 or less.
第１図は本発明になる化合物の質量分析スペクトルの分
子イオンピーク、第２図はその赤外線吸収スペクトル、
第３図はそのＮＭＲスペクトル、第４図及び第５図は類
似化合物のＮＭＲスペクトルである。Figure 1 shows the molecular ion peak of the mass spectrometry spectrum of the compound of the present invention, Figure 2 shows its infrared absorption spectrum,
FIG. 3 shows its NMR spectrum, and FIGS. 4 and 5 show NMR spectra of similar compounds.
Claims (1)
４′−アジノベンザル−２−メトキシアセトフェノン。 ２ ｐ−アジドベンズルアルデヒドと−２−メトキシア
セトフェノンとをアルカリ性化合物を触媒として反応さ
せることを特徴とする４′−アジノベンザル−２−メト
キシアセトフェノンの製造法。[Scope of Claims] 1 4'-Azinobenzal-2-methoxyacetophenone represented by the formula ▲ Numerical formula, chemical formula, table, etc. available ▼. 2. A method for producing 4'-azinobenzal-2-methoxyacetophenone, which comprises reacting p-azidobenzraldehyde and -2-methoxyacetophenone using an alkaline compound as a catalyst.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58069450A JPS6043382B2 (en) | 1983-04-20 | 1983-04-20 | 4'-azidobenzal-2-methoxyacetophenone and its production method |
| DE3415033A DE3415033C2 (en) | 1983-04-20 | 1984-04-19 | 4'-Azidobenzal-2-methoxyacetophenone, process for its preparation and photosensitive composition containing it |
| US06/886,353 US4698291A (en) | 1983-04-20 | 1986-07-17 | Photosensitive composition with 4-azido-2'-methoxychalcone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58069450A JPS6043382B2 (en) | 1983-04-20 | 1983-04-20 | 4'-azidobenzal-2-methoxyacetophenone and its production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59193859A JPS59193859A (en) | 1984-11-02 |
| JPS6043382B2 true JPS6043382B2 (en) | 1985-09-27 |
Family
ID=13402982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58069450A Expired JPS6043382B2 (en) | 1983-04-20 | 1983-04-20 | 4'-azidobenzal-2-methoxyacetophenone and its production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6043382B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1348690A1 (en) * | 2002-03-29 | 2003-10-01 | Toyo Gosei Kogyo Co., Ltd. | Cinnamaldehyde compound having an azido group |
-
1983
- 1983-04-20 JP JP58069450A patent/JPS6043382B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59193859A (en) | 1984-11-02 |
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