JPH0417987B2 - - Google Patents
Info
- Publication number
- JPH0417987B2 JPH0417987B2 JP57099961A JP9996182A JPH0417987B2 JP H0417987 B2 JPH0417987 B2 JP H0417987B2 JP 57099961 A JP57099961 A JP 57099961A JP 9996182 A JP9996182 A JP 9996182A JP H0417987 B2 JPH0417987 B2 JP H0417987B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- formula
- reaction
- pyrylium
- butanol
- 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 - Lifetime
Links
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 fluoroborate Chemical compound 0.000 description 3
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical class C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 3
- DLYSUUIMSFGXDL-UHFFFAOYSA-N 2-methyl-4,6-diphenylpyrylium Chemical class [O+]=1C(C)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 DLYSUUIMSFGXDL-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DKJFSVIHOOLBKY-UHFFFAOYSA-M 2-methyl-4,6-diphenylpyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.[O+]=1C(C)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 DKJFSVIHOOLBKY-UHFFFAOYSA-M 0.000 description 1
- ADPBOZWKPHDQAF-UHFFFAOYSA-N 2-methyl-4,6-diphenylthiopyrylium Chemical class [S+]=1C(C)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 ADPBOZWKPHDQAF-UHFFFAOYSA-N 0.000 description 1
- HEHGLKMZYJFACH-UHFFFAOYSA-M 2-methyl-4,6-diphenylthiopyrylium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.[S+]=1C(C)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 HEHGLKMZYJFACH-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- RGBVWCQARBEPPW-UHFFFAOYSA-N cyclobut-3-ene-1,2-dione Chemical compound O=C1C=CC1=O RGBVWCQARBEPPW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明は新規なピリリウム系染料およびその製
造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel pyrylium dye and a method for producing the same.
本発明の目的は新規なピリリウム系染料および
その製造方法を提供することにある。 An object of the present invention is to provide a new pyrylium dye and a method for producing the same.
本発明による染料は下記一般式(1)に示される。 The dye according to the present invention is represented by the following general formula (1).
（式中、Ｘは酸素原子または硫黄原子を表わす。）
本発明のピリリウム系染料は下記一般式(2)で示
される２−メチル−４，６−ジフエニルピリリウ
ム塩、２−メチル−４，６−ジフエニルチオピリ
リウム塩と３，４−ジヒドロキシ−３−シクロブ
テン−１，２−ジオンとを溶媒中で反応させるこ
とによつて容易に得ることができる。 (In the formula, X represents an oxygen atom or a sulfur atom.) The pyrylium dye of the present invention is a 2-methyl-4,6-diphenylpyrylium salt, a 2-methyl-4, , 6-diphenylthiopyrylium salt and 3,4-dihydroxy-3-cyclobutene-1,2-dione in a solvent.
式中、Ｘは酸素原子または硫黄原子を表わし、
Ｚ
はパークロレート、フルオボレート、スルフ
オアセテートなどのアニオンを表わす。 In the formula, X represents an oxygen atom or a sulfur atom,
Z represents an anion such as perchlorate, fluoroborate, sulfoacetate, etc.
一般式(2)で示される２−メチル−４，６−ジフ
エニルピリリウム塩はSchneiderらのBer誌54巻
2289頁（1921年）記載の方法によつて、また２−
メチル−４，６−ジフエニルチオピリリウム塩は
WizingerらのHelv.Chim.Acta誌39巻221頁
（1956年）の方法によつて得ることができる。 The 2-methyl-4,6-diphenylpyrylium salt represented by the general formula (2) is prepared by Schneider et al., Ber, Vol. 54.
By the method described on page 2289 (1921), and 2-
Methyl-4,6-diphenylthiopyrylium salt is
It can be obtained by the method described by Wizinger et al., Helv. Chim. Acta, Vol. 39, p. 221 (1956).
用いられる溶媒としては、広範な有機溶剤を使
用することができるが、好ましくは、エタノー
ル、ブタノール、ベンジルアルコールなどのアル
コール類、アセトニトリル、プロピオニトリル等
のニトリル類、酢酸などの有機カルボン酸類、無
水酢酸などの酸無水物が用いられる。また、ブタ
ノール、ベンジルアルコールなどにベンゼンなど
の芳香族炭化水素を混合することもできる。 As the solvent, a wide range of organic solvents can be used, but preferably alcohols such as ethanol, butanol and benzyl alcohol, nitrites such as acetonitrile and propionitrile, organic carboxylic acids such as acetic acid, and anhydrous Acid anhydrides such as acetic acid are used. Furthermore, aromatic hydrocarbons such as benzene can be mixed with butanol, benzyl alcohol, and the like.
反応系における原料化合物の割合は、３，４−
ジヒドロキシ−３−シクロブテン−１，２−ジオ
ンの１モルに対して一般式(2)で示されるピリリウ
ム塩またはチオピリリウム塩は1.0〜5.0当量モル
好ましくは1.5〜3.0当量モルである。反応溶媒
は、原料化合物の合計量１ｇに対し、0.5から100
ml、好ましくは２mlから10mlである。 The ratio of raw material compounds in the reaction system is 3,4-
The amount of pyrylium salt or thiopyrylium salt represented by general formula (2) is 1.0 to 5.0 equivalent moles, preferably 1.5 to 3.0 equivalent moles, per 1 mole of dihydroxy-3-cyclobutene-1,2-dione. The reaction solvent is used in an amount of 0.5 to 100% per 1 g of the total amount of raw material compounds
ml, preferably from 2 ml to 10 ml.
反応温度は25℃から200℃、好ましくは60℃か
ら140℃で行なわれ、反応時間は５分から30時間、
好ましくは20分から５時間である。 The reaction temperature is 25°C to 200°C, preferably 60°C to 140°C, and the reaction time is 5 minutes to 30 hours.
Preferably it is from 20 minutes to 5 hours.
また反応の促進のために、塩基を加えることが
出来る。具体的にはトリエチルアミン、ピリジ
ン、キノリン、酢酸ナトリウム、などの塩基を用
いることが出来る。 Furthermore, a base can be added to promote the reaction. Specifically, bases such as triethylamine, pyridine, quinoline, and sodium acetate can be used.
本発明の染料は、600nｍから1100nｍ附近まで
の領域において吸収を有しており、半導体レーザ
ーを光源とした電子写真プリンターの電子写真感
光材料や、半導体レーザーにより書き込みと読み
出しが可能な光デイスク用記録材料あるいは赤外
線カツトフイルターなどの分野でその有用性を期
待されるものである。 The dye of the present invention has absorption in the region from 600 nm to around 1100 nm, and can be used as an electrophotographic photosensitive material for electrophotographic printers using a semiconductor laser as a light source, and for optical disk recording that can be written and read by a semiconductor laser. It is expected to be useful in fields such as materials and infrared cut filters.
次に本発明のピリリウム染料およびチオピリリ
ウム染料製造のための実施例を示す。 Next, examples for producing pyrylium dyes and thiopyrylium dyes of the present invention will be shown.
実施例 １ ピリリウム染料（染料No.１）の製法。Example 1 Manufacturing method of pyrylium dye (dye No. 1).
（染料No.１）
100ml三ツ口フラスコに、３，４−ジヒドロキ
シ−３−シクロブテン−１，２−ジオン1.2ｇ
（0.0105モル）と、ｎ−ブタノール36mlを加え撹
拌しながら、100℃まで加熱し、溶解させた。キ
ノリン３ml、２−メチル−４，６−ジフエニルピ
リリウムパークロレート7.3ｇ（0.0211モル）お
よびベンゼン15mlを順次フラスコ内に加え、反応
を開始させた。反応は95〜110℃においてベンゼ
ン30ml、ブタノール20mlを分割添加しながら、水
を共沸留去させて、３時間30分行なつた。 (Dye No. 1) 1.2 g of 3,4-dihydroxy-3-cyclobutene-1,2-dione in a 100 ml three-necked flask
(0.0105 mol) and 36 ml of n-butanol were added and heated to 100° C. with stirring to dissolve. 3 ml of quinoline, 7.3 g (0.0211 mol) of 2-methyl-4,6-diphenylpyrylium perchlorate, and 15 ml of benzene were sequentially added into the flask to initiate the reaction. The reaction was carried out for 3 hours and 30 minutes at 95 to 110° C. while adding 30 ml of benzene and 20 ml of butanol in portions while azeotropically distilling off water.
反応液を冷却後吸引過し、ｎ−ブタノール30
mlで洗浄し、粗染料を得る。 The reaction solution was cooled, filtered by suction, and diluted with n-butanol 30
ml to obtain the crude dye.
粗染料を200mlのメタノールで５回煮沸過し、
その後、テトラヒドロフラン100mlで２回煮沸
過し染料No.１を得た。 The crude dye was boiled and filtered with 200ml of methanol 5 times.
Thereafter, the mixture was boiled and filtered twice with 100 ml of tetrahydrofuran to obtain Dye No. 1.
収量：1.9ｇ、収率：31.7％
融点：255〜258℃
元素分析：分子式C40H26O4
計算値 分析値
Ｃ 84.18 84.02
Ｈ 4.60 4.76
可視赤外吸収スペクトル：ジメチルフオルムア
ミド中
λnax ε
910nｍ 6.6×104
815nｍ 6.2×104
実施例 ２
チオピリリウム染料（染料No.２）の製法。Yield: 1.9g, yield: 31.7% Melting point: 255-258℃ Elemental analysis: Molecular formula C 40 H 26 O 4 Calculated value Analysis value C 84.18 84.02 H 4.60 4.76 Visible infrared absorption spectrum: λ nax ε 910 nm in dimethylformamide 6.6×10 4 815 nm 6.2×10 4 Example 2 Method for producing thiopyrylium dye (dye No. 2).
（染料No.２）
100ml三ツ口フラスコに３，４ジヒドロキシ−
３−シクロブテン−１，２−ジオン1.0ｇ
（0.0088モル）とｎ−ブタノール50mlを加え、撹
拌しながら100℃まで加熱し溶解させた。次にキ
ノリン2.5ml２−メチル−４，６−ジフエニルチ
オピリリウムパークロレート6.36ｇ（0.0176モ
ル）およびベンゼン10mlを順次フラスコ内に加え
反応を開始させた。反応は95〜110℃において、
ベンゼン30ml、ｎ−ブタノール10mlを分割添加し
ながら水を共沸留去させ、３時間行なつた。 (Dye No. 2) 3,4 dihydroxy in a 100ml three-necked flask
3-cyclobutene-1,2-dione 1.0g
(0.0088 mol) and 50 ml of n-butanol were added and heated to 100° C. with stirring to dissolve. Next, 2.5 ml of quinoline, 6.36 g (0.0176 mol) of 2-methyl-4,6-diphenylthiopyrylium perchlorate, and 10 ml of benzene were sequentially added into the flask to start the reaction. The reaction was carried out at 95-110℃.
Water was azeotropically distilled off while adding 30 ml of benzene and 10 ml of n-butanol in portions for 3 hours.
反応液を一晩放置した後、吸引過し、ｎ−ブ
タノール30mlで洗浄し、粗染料を得た。 After the reaction solution was left overnight, it was filtered under suction and washed with 30 ml of n-butanol to obtain a crude dye.
粗染料を200mlのメタノールで５回煮沸過し、
その後、テトラヒドロフラン100mlで２回煮沸
過し、染料No.２を得た。 The crude dye was boiled and filtered with 200ml of methanol 5 times.
Thereafter, it was boiled and filtered twice with 100 ml of tetrahydrofuran to obtain dye No. 2.
収量：1.36ｇ、収率：25.7％
融点：232.5〜235℃
元素分析：分子式C40H26O2S2
計算値 分析値
Ｃ 79.70 79.59
Ｈ 4.36 4.45
Ｓ 10.64 10.69
可視赤外吸収スペクトル：ジメチルフオルムア
ミド中
λnax ε
975nｍ 5.13×104
885nｍ 5.29×104 Yield: 1.36g, Yield: 25.7% Melting point: 232.5-235℃ Elemental analysis: Molecular formula C 40 H 26 O 2 S 2 Calculated value Analysis value C 79.70 79.59 H 4.36 4.45 S 10.64 10.69 Visible infrared absorption spectrum: Dimethylformamide Medium λ nax ε 975nm 5.13×10 4 885nm 5.29×10 4
第１図は染料No.１の赤外線吸収スペクトル、第
２図は染料No.１のジメチルフオルムアミド溶液の
可視赤外吸収スペクトルを示す説明図である。
FIG. 1 is an explanatory diagram showing the infrared absorption spectrum of dye No. 1, and FIG. 2 is an explanatory diagram showing the visible and infrared absorption spectrum of a dimethylformamide solution of dye No. 1.
Claims (1)
で示されるピリリウム系染料。 ２ 下記一般式(2) （式中、Ｘは酸素原子または硫黄原子を表わし、
Ｚ はアニオンを表わす。） で示されるピリリウム系塩と３，４−ジヒドロキ
シ−３−シクロブテン−１，２−ジオンとを反応
させることを特徴とする下記一般式(1) （式中、Ｘは酸素原子または硫黄原子を表わす。）
で示されるピリリウム系染料の製造方法。[Claims] 1 The following general formula (1) (In the formula, X represents an oxygen atom or a sulfur atom.)
A pyrylium dye indicated by . 2 General formula (2) below (In the formula, X represents an oxygen atom or a sulfur atom,
Z represents an anion. ) The following general formula (1) is characterized by reacting a pyrylium salt represented by the formula with 3,4-dihydroxy-3-cyclobutene-1,2-dione. (In the formula, X represents an oxygen atom or a sulfur atom.)
A method for producing pyrylium dye shown in
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57099961A JPS58217558A (en) | 1982-06-12 | 1982-06-12 | New pyrylium dye and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57099961A JPS58217558A (en) | 1982-06-12 | 1982-06-12 | New pyrylium dye and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58217558A JPS58217558A (en) | 1983-12-17 |
| JPH0417987B2 true JPH0417987B2 (en) | 1992-03-26 |
Family
ID=14261270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57099961A Granted JPS58217558A (en) | 1982-06-12 | 1982-06-12 | New pyrylium dye and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58217558A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113564943A (en) * | 2021-07-09 | 2021-10-29 | 天津工业大学 | Electronic mediator enhanced indigo whole-cell reduction dyeing method |
-
1982
- 1982-06-12 JP JP57099961A patent/JPS58217558A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58217558A (en) | 1983-12-17 |
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