JPH0733766A - Diamino-s-triazine compound having imidazole ring and method for preventing copper from rusting using the same compound - Google Patents

Diamino-s-triazine compound having imidazole ring and method for preventing copper from rusting using the same compound

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Publication number
JPH0733766A
JPH0733766A JP5202584A JP20258493A JPH0733766A JP H0733766 A JPH0733766 A JP H0733766A JP 5202584 A JP5202584 A JP 5202584A JP 20258493 A JP20258493 A JP 20258493A JP H0733766 A JPH0733766 A JP H0733766A
Authority
JP
Japan
Prior art keywords
compound
diamino
copper
triazine
formula
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.)
Pending
Application number
JP5202584A
Other languages
Japanese (ja)
Inventor
Natsuo Sawa
夏雄 澤
Yoshiyuki Tsuda
美幸 津田
Shuichi Nomura
修一 野村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shikoku Chemicals Corp
Original Assignee
Shikoku Chemicals Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shikoku Chemicals Corp filed Critical Shikoku Chemicals Corp
Priority to JP5202584A priority Critical patent/JPH0733766A/en
Publication of JPH0733766A publication Critical patent/JPH0733766A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To obtain a new compound useful as a rust preventing agent for copper and alloys thereof, a curing agent or a curing accelerator for epoxy resins. CONSTITUTION:This compound is expressed by formula I [R1 is CH2CH2, CH2 CH2CH2CH2 or 1,3- or 1,4-phenylene; R2 is H or methyl), e.g. p-(4'- methylimidazolyl-2')-phenylene-[4'',6''-diamino-1'',3'',5''-s-triazine ]-(2''). The compound expressed by formula I is obtained by reacting a compound, expressed by formula II and having nitrile group and the diamino-s-triazine ring with a 1,2-diamine expressed by formula III in the presence of a simple substance of sulfur, providing a compound expressed by formula IV and then reacting the resultant compound expressed by formula IV in a solvent (e.g. DMF) by using a copper compound (e.g. basic copper carbonate) at 120-200 deg.C. The imidazoline ring is dehydrogenated and converted into the imidazole ring by heating the reactional mixture with the copper compound capable of producing copper oxide as a catalyst. Thereby, the compound expressed by formula I is obtained.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は新規なイミダゾール環を
有するジアミノ−ｓ−トリアジン化合物に関するもので
あり、本発明化合物は、銅あるいは銅合金の防錆剤及び
エポキシ樹脂の硬化剤あるいは硬化促進剤として有用で
ある。FIELD OF THE INVENTION The present invention relates to a novel diamino-s-triazine compound having an imidazole ring. The compound of the present invention is a rust preventive for copper or copper alloys and a curing agent or curing accelerator for epoxy resins. Is useful as

【０００２】[0002]

【従来の技術】イミダゾール化合物を銅あるいは銅合金
の防錆剤として用いる方法としては、特開平２−９３０
７９号に２位長鎖アルキルイミダゾール化合物と銅イオ
ンを含む処理液に接触させる方法が開示されている。ま
た、多くのイミダゾール化合物がエポキシ樹脂の硬化剤
あるいは硬化促進剤として使用されており、特に4,6-ジ
アミノ−1,3,5-s-トリアジンと２−メチルイミダゾール
をエタンで連結した化合物〔商品名：２ＭＡ，四国化成
工業（株）製〕は、所謂一液性エポキシ樹脂組成物とし
て用いた場合に保存安定性がよいので、電気絶縁塗料等
の分野に多く使用されている。2. Description of the Related Art As a method of using an imidazole compound as a rust preventive for copper or copper alloys, JP-A-2-930 is known.
No. 79 discloses a method of contacting a treatment solution containing a 2-position long-chain alkylimidazole compound and copper ions. Further, many imidazole compounds are used as a curing agent or curing accelerator for epoxy resins, and in particular, a compound in which 4,6-diamino-1,3,5-s-triazine and 2-methylimidazole are linked with ethane [ The product name: 2MA, manufactured by Shikoku Kasei Kogyo Co., Ltd.] has good storage stability when used as a so-called one-component epoxy resin composition, and is therefore widely used in the field of electrical insulating paints and the like.

【０００３】[0003]

【発明が解決しようとする課題】本発明の目的は、同一
分子内にトリアジン環とイミダゾ−ル環を有する新規な
化合物を提供し、この新規化合物を用いて銅あるいは銅
合金を防錆する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel compound having a triazine ring and an imidazole ring in the same molecule, and to use this novel compound to prevent rusting of copper or copper alloy. To provide.

【０００４】[0004]

【課題を解決するための手段】本発明者等は、このよう
な事情に鑑み鋭意研究を重ねた結果、分子の一方の末端
にイミダゾリン環を有し、他方の末端にジアミノ−ｓ−
トリアジン環を有する化合物を加熱した際に酸化銅を発
生する銅化合物と共に加熱することにより、イミダゾリ
ン環が脱水素してイミダゾール環に変わり、化２で示さ
れる化合物が得られることを見い出し、本発明を完遂す
るに至った。Means for Solving the Problems As a result of intensive studies conducted by the present inventors in view of such circumstances, the present inventors have an imidazoline ring at one end of a molecule and diamino-s-
It was found that by heating a compound having a triazine ring together with a copper compound that generates copper oxide when heated, the imidazoline ring is dehydrogenated and converted into an imidazole ring, and the compound represented by Chemical formula 2 is obtained. Has been completed.

【０００５】[0005]

【化２】 [Chemical 2]

【０００６】本発明化合物の出発原料となるニトリル基
とジアミノ−ｓ−トリアジン環を有する化合物は、英国
特許第６４２４０９号、有機合成化学、第２４巻、１２
５〜１２６頁（1966年）及びビュレチン・オブ・ケミカ
ル・ソサイアティ・ジャパン（Bull. Chem. Soc. Japa
n）、第３８巻、１８２０〜１８２４頁（1965年）に記
載の方法により得られ、これを反応式で表せば化３に示
すとおりである。The compound having a nitrile group and a diamino-s-triazine ring as a starting material for the compound of the present invention is described in British Patent No. 642409, Organic Synthetic Chemistry, Vol. 24, 12.
Pages 5 to 126 (1966) and Bulletin of Chemical Society Japan (Bull. Chem. Soc. Japa
n), Vol. 38, pp. 1820-1824 (1965), and the reaction formula is shown in Chemical formula 3.

【０００７】[0007]

【化３】 [Chemical 3]

【０００８】次いで前記のニトリル基とジアミノ−ｓ−
トリアジン環を有する化合物を単体硫黄の存在下、１，
２−ジアミンと反応させることにより、分子の一方の末
端にイミダゾリン環を有し、他方の末端にジアミノ−ｓ
−トリアジン環を有する化合物が得られる。この反応を
式で表せば、化４に示すとおりである。（特願平４−３
５４３１２号参照）Then, the above-mentioned nitrile group and diamino-s-
In the presence of elemental sulfur, a compound having a triazine ring
By reacting with 2-diamine, it has an imidazoline ring at one end of the molecule and diamino-s at the other end.
A compound having a triazine ring is obtained. This reaction is represented by the formula 4 below. (Japanese Patent Application No. 4-3
(See No. 54312)

【０００９】[0009]

【化４】 [Chemical 4]

【００１０】本発明化合物の製造に当たって、イミダゾ
リン環をイミダゾール環に変えるためには、触媒として
加熱した時に酸化銅を発生する銅化合物が用いられる。
この銅化合物とイミダゾリン環を有するジアミノ−ｓ−
トリアジン環化合物を比較的高沸点の溶剤中で１２０な
いし２００℃の温度に加熱し、２時間程度反応させ、得
られる不溶性の銅塩を濾取し、これを鉱酸酸性水に溶か
し、この溶液に硫化水素を吹き込むか、または水硫化ナ
トリウムを添加して脱銅したのち、硫化銅を濾別し、得
られた濾液を常法で処理することにより、本発明化合物
が得られる。In the production of the compound of the present invention, in order to change the imidazoline ring into an imidazole ring, a copper compound which generates copper oxide when heated is used as a catalyst.
This copper compound and diamino-s-having an imidazoline ring
The triazine ring compound is heated to a temperature of 120 to 200 ° C. in a solvent having a relatively high boiling point, reacted for about 2 hours, the resulting insoluble copper salt is filtered off, and dissolved in acidic water of mineral acid Hydrogen sulfide is blown into the mixture, or sodium hydrosulfide is added to remove copper, the copper sulfide is filtered off, and the obtained filtrate is treated by a conventional method to obtain the compound of the present invention.

【００１１】本発明化合物を製造するために用いられる
銅化合物の代表的なものとしては、水酸化銅、炭酸銅あ
るいは塩基性炭酸銅等である。また、銅化合物の代わり
に塩化銅、硫酸銅及び硝酸銅等の銅塩を用いて、イミダ
ゾリン環を有するジアミノ−ｓ−トリアジン環化合物と
銅塩の銅錯体を作ったのち、この銅錯体のアニオンを炭
酸ナトリウムを用いて炭酸イオンに変えるか、または水
酸化ナトリウムを用いて水酸イオンに変えたのち、加熱
しても本発明化合物を得ることができる。また本発明化
合物の製造に当たって用いられる比較的高沸点の溶剤の
代表的なものとしては、ＤＭＦ、ＤＭＳＯ及びエチレン
グリコール等である。Typical examples of the copper compound used for producing the compound of the present invention are copper hydroxide, copper carbonate, basic copper carbonate and the like. Moreover, after using a copper salt such as copper chloride, copper sulfate, and copper nitrate instead of the copper compound to form a copper complex of the diamino-s-triazine ring compound having an imidazoline ring and the copper salt, the anion of the copper complex is obtained. The compound of the present invention can also be obtained by heating after converting to a carbonate ion using sodium carbonate or a hydroxide ion using sodium hydroxide. Typical examples of the solvent having a relatively high boiling point used in the production of the compound of the present invention are DMF, DMSO, ethylene glycol and the like.

【００１２】代表的な本発明のイミダゾール環を有する
ジアミノ−ｓ−トリアジン化合物及びその物性は、次に
示すとおりである。Representative diamino-s-triazine compounds having an imidazole ring of the present invention and their physical properties are as follows.

【００１３】２−（イミダゾリル-2')−エチレン−
〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕−(2")2- (imidazolyl-2 ')-ethylene-
[4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2")

【００１４】[0014]

【化５】 [Chemical 5]

【００１５】塩基性無色結晶。融点：２４２〜２５３℃ 水とメタノールの混合溶剤に熱時易溶。水、メタノー
ル、ＤＭＦ及びメチルセロソルブに難溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.４２〜0.５８
（Ｉ2 発色） ＩＲ(KBr):ν 3476(16.0),3332(18.9),3100(14.0),2363
(28.8),1682(19.6),1640(12.1),1565(12.8),1539(11.
4),1462(21.2),1445(17.0),1410(23.2),1333(32.3),116
7(34.1),1105(30.7),1019(34.7),986(38.2), 841(38.
6), 810(34.7), 745(32.0), 722(37.4),650(40.4), 594
(33.8), 565(41.9), 467(39.4), 409(45.9) cm-1（カッ
コ内は透過率％を示す） ＮＭＲ(d6 -DMSO): δ6.93と6.73,br.s,2H( イミダゾー
ルの４と５位);6.56,s,4H(アミノ基);2.99〜2.65,m,4H
(エチレン基) Ｍａｓｓ：m/e 205( M+ ),138,125,120,111, 95(基準ピ
ーク),81,68,54,43,28Basic colorless crystals. Melting point: 242 to 253 ° C. Soluble in a mixed solvent of water and methanol when heated. Poorly soluble in water, methanol, DMF and methyl cellosolve. TLC (silica, methanol): Rf 0.42 to 0.58
(I 2 color development) IR (KBr): ν 3476 (16.0), 3332 (18.9), 3100 (14.0), 2363
(28.8), 1682 (19.6), 1640 (12.1), 1565 (12.8), 1539 (11.
4), 1462 (21.2), 1445 (17.0), 1410 (23.2), 1333 (32.3), 116
7 (34.1), 1105 (30.7), 1019 (34.7), 986 (38.2), 841 (38.
6), 810 (34.7), 745 (32.0), 722 (37.4), 650 (40.4), 594
(33.8), 565 (41.9), 467 (39.4), 409 (45.9) cm -1 (% transmittance in parentheses) NMR (d 6 -DMSO): δ6.93 and 6.73, br.s, 2H (The 4th and 5th position of imidazole); 6.56, s, 4H (amino group); 2.99 to 2.65, m, 4H
(Ethylene group) Mass: m / e 205 (M + ), 138,125,120,111, 95 (reference peak), 81,68,54,43,28

【００１６】２−（4'−メチルイミダゾリル-2')−エチ
レン−〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕−
(2")2- (4'-Methylimidazolyl-2 ')-ethylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-
(2 ")

【００１７】[0017]

【化６】 [Chemical 6]

【００１８】塩基性無色結晶。融点：Ｃａ．２５４℃。
水及びメタノールに可溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.４０〜0.５２
（Ｉ2 発色） ＩＲ(KBr):ν 3845(33.9),3808(34.3),3550(22.9),3472
(16.5),3416(14.1),3123(30.9),1653(34.5),1644(34.
8),1620(38.2),1563(38.3),1545(36.5),1462(45.0), 81
8(50.5), 615(44.1), 478(42.9),401(40.9) cm-1 ＮＭＲ(d6 -DMSO): δ6.72,br.s,1H (イミダゾールの５
位);6.57,s,4H(アミノ基);2.86,m,4H( エチレン基);2.1
2,S,3H(メチル基） Ｍａｓｓ：m/e 219( M+ ),138,125,109(基準ピーク),9
5,81,68,54,43,28Basic colorless crystals. Melting point: Ca. 254 ° C.
Soluble in water and methanol. TLC (silica, methanol): Rf 0.40 to 0.52
(I 2 color development) IR (KBr): ν 3845 (33.9), 3808 (34.3), 3550 (22.9), 3472
(16.5), 3416 (14.1), 3123 (30.9), 1653 (34.5), 1644 (34.
8), 1620 (38.2), 1563 (38.3), 1545 (36.5), 1462 (45.0), 81
8 (50.5), 615 (44.1), 478 (42.9), 401 (40.9) cm -1 NMR (d 6 -DMSO): δ6.72, br.s, 1H (5 of imidazole
Position); 6.57, s, 4H (amino group); 2.86, m, 4H (ethylene group); 2.1
2, S, 3H (methyl group) Mass: m / e 219 (M + ), 138,125,109 (reference peak), 9
5,81,68,54,43,28

【００１９】４−（イミダゾリル-2')−ｎ−ブチレン−
〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕−(2")4- (imidazolyl-2 ')-n-butylene-
[4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2")

【００２０】[0020]

【化７】 [Chemical 7]

【００２１】塩基性無色結晶。融点：２４８〜２６０
℃。水及びメタノールに可溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.４５〜0.６０
（Ｉ2 発色） ＩＲ(KBr):ν 3405( 8.0),3324( 9.0),2979( 9.0),2917
( 9.2),2664(21.2),2361(25.3),1678( 6.8),1653( 2.
2),1543( 1.3),1445( 6.6),1404(10.9),1381(19.7),134
8(22.7),1267(22.4),1206(28.1),1171(26.5),1148(28.
6),1105(17.0),1069(29.5),1013(20.6),967(30.3), 922
(36.7), 880(35.4), 822(21.7), 745(21.7),706(26.4),
673(34.9), 650(33.2), 596(24.1), 573(35.8),413(3
8.4) cm-1 ＮＭＲ(d6 -DMSO): δ6.83,s,2H(イミダゾールの４と５
位);6.55,s,4H(アミノ基);2.63〜2.37,m,4H(１と４位の
メチレン基);1.65,m,4H(２と３位のメチレン基) Ｍａｓｓ：m/e 233( M+ ),204,152,139,138,125,109,9
6,95(基準ピーク),82,81,68,54,43,28Basic colorless crystals. Melting point: 248-260
° C. Soluble in water and methanol. TLC (silica, methanol): Rf 0.45 to 0.60
(I 2 color development) IR (KBr): ν 3405 (8.0), 3324 (9.0), 2979 (9.0), 2917
(9.2), 2664 (21.2), 2361 (25.3), 1678 (6.8), 1653 (2.
2), 1543 (1.3), 1445 (6.6), 1404 (10.9), 1381 (19.7), 134
8 (22.7), 1267 (22.4), 1206 (28.1), 1171 (26.5), 1148 (28.
6), 1105 (17.0), 1069 (29.5), 1013 (20.6), 967 (30.3), 922
(36.7), 880 (35.4), 822 (21.7), 745 (21.7), 706 (26.4),
673 (34.9), 650 (33.2), 596 (24.1), 573 (35.8), 413 (3
8.4) cm -1 NMR (d 6 -DMSO): δ6.83, s, 2H (imidazole 4 and 5
Position); 6.55, s, 4H (amino group); 2.63 to 2.37, m, 4H (methylene group at 1 and 4 positions); 1.65, m, 4H (methylene group at 2 and 3 positions) Mass: m / e 233 (M + ), 204,152,139,138,125,109,9
6,95 (reference peak), 82,81,68,54,43,28

【００２２】４−（4'−メチルイミダゾリル-2')−ｎ−
ブチレン−〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕
−(2")4- (4'-methylimidazolyl-2 ')-n-
Butylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]
-(2 ")

【００２３】[0023]

【化８】 [Chemical 8]

【００２４】塩基性無色結晶。融点：２６３〜２７３
℃。 水とメタノールの混合溶剤に易溶。水に可溶。メタノー
ルに難溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.３０〜0.５０
（Ｉ2 発色） ＩＲ(KBr):ν 3843(23.4),3409(12.6),3332(12.9),2944
(13.8),1682(15.9),1653( 5.6),1547( 3.2),1462(15.
6),1443(13.0),1404(19.5),1347(30.3),1269(30.3),120
6(35.6),1169(34.8),1115(29.4),1013(34.8), 822(34.
4), 756(37.6), 712(42.6), 596(37.6),428(49.9) cm-1 ＮＭＲ(d6 -DMSO): δ 6.50,br.s,5H(イミダゾールの５
位とアミノ基);2.32,m,4H(１と４位のメチレン基);2.0
7,s,3H(メチル基);1.62,m,4H(２と３位のメチレン基) Ｍａｓｓ：m/e 247( M+ ),204,152,139,138,125,110,10
9(基準ピーク),96,85,68,54,43,28Basic colorless crystals. Melting point: 263-273
° C. Easily soluble in a mixed solvent of water and methanol. Soluble in water. Poorly soluble in methanol. TLC (silica, methanol): Rf 0.30 to 0.50
(I 2 color development) IR (KBr): ν 3843 (23.4), 3409 (12.6), 3332 (12.9), 2944
(13.8), 1682 (15.9), 1653 (5.6), 1547 (3.2), 1462 (15.
6), 1443 (13.0), 1404 (19.5), 1347 (30.3), 1269 (30.3), 120
6 (35.6), 1169 (34.8), 1115 (29.4), 1013 (34.8), 822 (34.
4), 756 (37.6), 712 (42.6), 596 (37.6), 428 (49.9) cm -1 NMR (d 6 -DMSO): δ 6.50, br.s, 5H (5 of imidazole
Position and amino group); 2.32, m, 4H (methylene group at 1 and 4 positions); 2.0
7, s, 3H (methyl group); 1.62, m, 4H (methylene group at 2 and 3 positions) Mass: m / e 247 (M + ), 204,152,139,138,125,110,10
9 (reference peak), 96,85,68,54,43,28

【００２５】ｍ−（イミダゾリル-2')−フェニレン−
〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕−(2")M- (imidazolyl-2 ')-phenylene-
[4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2")

【００２６】[0026]

【化９】 [Chemical 9]

【００２７】塩基性無色結晶。融点：２８６〜２９５℃ メタノール、ＤＭＦ及びＤＭＳＯに熱時可溶、水に難
溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.６０〜0.７８
（Ｉ2 発色） ＩＲ(KBr):ν 3860(40.1),3845(40.2),3808(40.6),3681
(41.4),3457(23.6),3359(23.9),3216(28.7),3115(30.
2),2921(37.2),2367(47.4),2344(47.8),1659(21.4),162
4(17.9),1545(12.5),1495(42.3),1445(37.8),1420(30.
3),1387(31.8),1316(50.5),1256(49.5),1113(48.6),107
6(50.2), 990(52.6), 967(48.5), 918(50.9),884(52.
5), 808(40.3), 766(46.4), 735(49.6), 714(39.9),685
(51.2), 621(49.5), 575(51.6) cm-1 ＮＭＲ(d6 -DMSO): δ8.98,s,1H(フェニレン基の２位);
8.33,8.20 及び8.00,3本のm,2H( フェニレン基の４と６
位);7.70,7.57 及び7.44,3本のs,1H( フェニレン基の５
位);7.20,s,2H(イミダゾールの４と５位);6.83,br.S,4H
( アミン基) Ｍａｓｓ：m/e 253( M+ , 基準ピーク),210,185,170,16
9,142,129,102,85,76,68,43Basic colorless crystals. Melting point: 286 to 295 ° C Soluble in methanol, DMF and DMSO when hot, and slightly soluble in water. TLC (silica, methanol): Rf 0.60 to 0.78
(I 2 color development) IR (KBr): ν 3860 (40.1), 3845 (40.2), 3808 (40.6), 3681
(41.4), 3457 (23.6), 3359 (23.9), 3216 (28.7), 3115 (30.
2), 2921 (37.2), 2367 (47.4), 2344 (47.8), 1659 (21.4), 162
4 (17.9), 1545 (12.5), 1495 (42.3), 1445 (37.8), 1420 (30.
3), 1387 (31.8), 1316 (50.5), 1256 (49.5), 1113 (48.6), 107
6 (50.2), 990 (52.6), 967 (48.5), 918 (50.9), 884 (52.
5), 808 (40.3), 766 (46.4), 735 (49.6), 714 (39.9), 685
(51.2), 621 (49.5), 575 (51.6) cm -1 NMR (d 6 -DMSO): δ8.98, s, 1H (2nd position of the phenylene group);
8.33,8.20 and 8.00,3 m, 2H (phenylene groups 4 and 6
Position); 7.70,7.57 and 7.44,3 s, 1H (5 of the phenylene group
); 7.20, s, 2H (4th and 5th of imidazole); 6.83, br.S, 4H
(Amine group) Mass: m / e 253 (M + , reference peak), 210,185,170,16
9,142,129,102,85,76,68,43

【００２８】ｍ−（４'-メチルイミダゾリル-2')−フェ
ニレン−（4",6"-ジアミノ-1",3",5"-s-トリアジン）−
(2")M- (4'-methylimidazolyl-2 ')-phenylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-
(2 ")

【００２９】[0029]

【化１０】 [Chemical 10]

【００３０】塩基性無色結晶。融点：ｃａ．３２０℃ メタノール、ＤＭＦ及びＤＭＳＯに熱時可溶、水に難
溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.６２〜0.７８
（Ｉ2 発色） ＩＲ(KBr):ν 3677(32.7),3652(32.1),3434(20.1),3341
(15.9),3168(13.6),2363(37.1),1673(19.6),1647(11.
0),1541( 2.6),1437(21.1),1404(18.6),1381(19.6),125
2(37.4),1082(37.2),1028(40.9),986(40.9), 824(36.
3), 803(36.9), 747(41.3), 712(37.1),675(38.5), 635
(37.3), 617(39.2), 581(40.1), 558(39.7),529(42.3),
421(46.1)cm-1 ＮＭＲ(d6 -DMSO): δ8.84,s,1H(フェニレン基の２位);
8.24,8.12,8.03及び7.90 4本のm,2H( フェニレン基の４と６位);7.60,7.46 及び
7.34,３本のs,1H( フェニレン基の５位);6.83,br.s,1H
( イミダゾールの５位);6.75,br.s,4H( アミン基);2.2
3,s,3H(メチル基) Ｍａｓｓ：m/e 267( M+ , 基準ピーク),239,224,213,18
3,182,157,142,129,102,85,82,68,55,54,44,28Basic colorless crystals. Melting point: ca. 320 ℃ Soluble in methanol, DMF and DMSO when hot, hardly soluble in water. TLC (silica, methanol): Rf 0.62 to 0.78
(I 2 color development) IR (KBr): ν 3677 (32.7), 3652 (32.1), 3434 (20.1), 3341
(15.9), 3168 (13.6), 2363 (37.1), 1673 (19.6), 1647 (11.
0), 1541 (2.6), 1437 (21.1), 1404 (18.6), 1381 (19.6), 125
2 (37.4), 1082 (37.2), 1028 (40.9), 986 (40.9), 824 (36.
3), 803 (36.9), 747 (41.3), 712 (37.1), 675 (38.5), 635
(37.3), 617 (39.2), 581 (40.1), 558 (39.7), 529 (42.3),
421 (46.1) cm -1 NMR (d 6 -DMSO): δ8.84, s, 1H (2nd position of phenylene group);
8.24,8.12,8.03 and 7.90 4 m, 2H (positions 4 and 6 of the phenylene group); 7.60,7.46 and
7.34,3 s, 1H (5th position of phenylene group); 6.83, br.s, 1H
(5th position of imidazole); 6.75, br.s, 4H (amine group); 2.2
3, s, 3H (methyl group) Mass: m / e 267 (M + , reference peak), 239,224,213,18
3,182,157,142,129,102,85,82,68,55,54,44,28

【００３１】ｐ−（イミダゾリル-2')−フェニレン−
〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕−(2")P- (imidazolyl-2 ')-phenylene-
[4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2")

【００３２】[0032]

【化１１】 [Chemical 11]

【００３３】塩基性無色結晶。融点：３１９〜３２７℃ 熱メチルセロソルブに可溶、水に難溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.６８〜0.８０
（Ｉ2 発色） ＩＲ(KBr):ν 3675(39.4),3652(39.0),3480(27.4),3322
(28.1),3181(27.1),3137(25.7),1667(28.0),1632(16.
1),1576(33.5),1555(17.4),1528(12.6),1447(32.3),143
5(29.0),1402(32.1),1250(46.3),1173(51.6),1107(49.
1), 961(52.6), 905(52.9), 864(51.2),816(42.8), 787
(55.0), 718(52.3), 583(53.7), 455(46.8),423(48.6)
cm-1 ＮＭＲ(d6 -DMSO): δ8.38と8.24,2本のm,2H( フェニレ
ン基の２と６位);8.07と7.92,2本のm,2H( フェニレン基
の３と５位);7.17,s,2H(イミダゾールの４と５位);6.7
2,br.s,4H( アミン基） Ｍａｓｓ：m/e 253( M+ , 基準ピーク),226,210,185,17
0,142,129,102,85,68,43Basic colorless crystals. Melting point: 319 to 327 ° C. Soluble in hot methyl cellosolve, hardly soluble in water. TLC (silica, methanol): Rf 0.68 to 0.80
(I 2 color development) IR (KBr): ν 3675 (39.4), 3652 (39.0), 3480 (27.4), 3322
(28.1), 3181 (27.1), 3137 (25.7), 1667 (28.0), 1632 (16.
1), 1576 (33.5), 1555 (17.4), 1528 (12.6), 1447 (32.3), 143
5 (29.0), 1402 (32.1), 1250 (46.3), 1173 (51.6), 1107 (49.
1), 961 (52.6), 905 (52.9), 864 (51.2), 816 (42.8), 787
(55.0), 718 (52.3), 583 (53.7), 455 (46.8), 423 (48.6)
cm -1 NMR (d 6 -DMSO): δ 8.38 and 8.24, 2 m, 2H (positions 2 and 6 of phenylene group); 8.07 and 7.92, 2 m, 2H (3 and 5 of phenylene group) Position); 7.17, s, 2H (4th and 5th position of imidazole); 6.7
2, br.s, 4H (amine group) Mass: m / e 253 (M + , reference peak), 226,210,185,17
0,142,129,102,85,68,43

【００３４】ｐ−（４'-メチルイミダゾリル-2')−フェ
ニレン−〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕−
(2")P- (4'-Methylimidazolyl-2 ')-phenylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-
(2 ")

【００３５】[0035]

【化１２】 [Chemical 12]

【００３６】塩基性無色結晶。融点：３１０〜３３１℃ メタノール、メチルセロソルブ、ＤＭＦ及びＤＭＳＯに
熱時可溶、水に難溶。 ＴＬＣ（シリカ、メタノール）：Ｒｆ0.６８〜0.８２ ＩＲ(KBr):ν 3858(30.8),3845(30.9),3528(27.9),3403
(22.5),3318(25.7),2344(37.9),1659(32.5),1620(27.
0),1607(28.1),1582(30.9),1545(14.0),1433(32.1),139
9(26.7),1138(44.6),1090(44.0),965(44.9), 907(44.
5), 860(46.6), 818(39.2), 716(46.5),639(47.9), 515
(51.9), 451(53.8) cm-1 ＮＭＲ(d6 -DMSO): δ8.35と8.21,2本のs,2H（フェニレ
ン基の３と５位);8.01と7.87,2本のs,2H（フェニレン基
の２と６位);6.70,br.S,4H(アミノ基);2.23,br.S,3H
（メチル基) Ｍａｓｓ：m/e 267( M+ , 基準ピーク),239,226,213,19
9,184,183,182,157,142,129,128,102,85,68,54,43Basic colorless crystals. Melting point: 310 to 331 ° C Soluble in methanol, methyl cellosolve, DMF and DMSO when hot, and slightly soluble in water. TLC (silica, methanol): Rf 0.68 to 0.82 IR (KBr): ν 3858 (30.8), 3845 (30.9), 3528 (27.9), 3403
(22.5), 3318 (25.7), 2344 (37.9), 1659 (32.5), 1620 (27.
0), 1607 (28.1), 1582 (30.9), 1545 (14.0), 1433 (32.1), 139
9 (26.7), 1138 (44.6), 1090 (44.0), 965 (44.9), 907 (44.
5), 860 (46.6), 818 (39.2), 716 (46.5), 639 (47.9), 515
(51.9), 451 (53.8) cm -1 NMR (d 6 -DMSO): δ8.35 and 8.21,2 s, 2H (3 and 5 positions of the phenylene group); 8.01 and 7.87,2 s, 2H (positions 2 and 6 of the phenylene group); 6.70, br.S, 4H (amino group); 2.23, br.S, 3H
(Methyl group) Mass: m / e 267 (M + , reference peak), 239,226,213,19
9,184,183,182,157,142,129,128,102,85,68,54,43

【００３７】[0037]

【作用】通常、イミダゾリン環をイミダゾール環に変え
るには、ニッケル触媒による脱水素反応を採用するのが
一般的であるが、本発明化合物の前駆体であるイミダゾ
リン環を有するジアミノ−ｓ−トリアジン化合物はニッ
ケル触媒では脱水素しない。このため本発明の実施にお
いては、ニッケル触媒の代わりに加熱した際に酸化銅を
形成しうる銅化合物を用い、酸化的脱水素反応を起こす
ことにより、イミダゾリン環をイミダゾール環に変え
る。In general, a nickel-catalyzed dehydrogenation reaction is generally used to convert an imidazoline ring into an imidazole ring. Does not dehydrogenate over nickel catalysts. Therefore, in the practice of the present invention, a copper compound capable of forming copper oxide when heated is used in place of the nickel catalyst to cause an oxidative dehydrogenation reaction to convert the imidazoline ring into an imidazole ring.

【００３８】[0038]

【実施例】【Example】

（実施例１）ｐ−（イミダゾリニル-2')−フェニレン−
〔4",6"-ジアミノ-1",3",5"-s-トリアジン〕−(2")１０
ｇ、塩基性炭酸銅１７．５ｇ、無水炭酸ナトリウム２．
５ｇ及びＤＭＦ３０mlの４者を１４０〜１５０℃の温度
範囲で２時間攪拌加熱したのち、放冷した。反応混合物
を濾過し、ウグイス色の銅塩を濾取して水洗したのち、
充分量の塩酸水と共に加熱し、放冷して析出する赤色物
質１４．３ｇを濾取した。(Example 1) p- (imidazolinyl-2 ')-phenylene-
[4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2") 10
g, basic copper carbonate 17.5 g, anhydrous sodium carbonate 2.
5 g and 30 ml of DMF were stirred and heated in a temperature range of 140 to 150 ° C. for 2 hours, and then allowed to cool. The reaction mixture was filtered, and the Uguis color copper salt was collected by filtration and washed with water.
The mixture was heated with a sufficient amount of hydrochloric acid water, allowed to cool, and 14.3 g of a precipitated red substance was collected by filtration.

【００３９】次いで、この赤色物質に充分量の塩酸水を
加えて加熱し、さらに水硫化ナトリウムを加えて脱銅し
て硫化銅を濾別し、濾液を乾固した。この乾固物にメタ
ノールを加えてメタノールに不溶の結晶を濾取し、水再
結晶を２回行って、粗目的物の塩酸塩の結晶５．５ｇを
得た。一方、メタノール濾液を乾固し、アセトン洗浄し
たのち水再結濾液の乾固物と併せて、水再結して粗目的
物の塩酸塩の結晶２．２５ｇを得た。Then, a sufficient amount of hydrochloric acid water was added to the red substance and heated, sodium hydrosulfide was further added to remove copper, copper sulfide was filtered off, and the filtrate was dried to dryness. Methanol was added to this dried solid product, and crystals insoluble in methanol were collected by filtration and recrystallized twice with water to obtain 5.5 g of crystals of a hydrochloride as a crude target product. On the other hand, the methanol filtrate was dried, washed with acetone, and then combined with the dried substance of the water reconstituted filtrate and reconstituted with water to obtain 2.25 g of crystals of a hydrochloride as a crude target substance.

【００４０】前記の両結晶を併せて、炭酸ナトリウム水
溶液と加熱し、析出する粗目的物のｐ−（イミダゾリル
-2')−フェニレン−〔4",6"-ジアミノ-1",3",5"-s-トリ
アジン〕−(2")〔以下、Ｚ６４Ａという〕６．５ｇを濾
取した。この粗目的物は微量の前駆物質を含むことがＴ
ＬＣで判明した。そこで、粗目的物をメタノールとメチ
ルセロソルブの混合溶液に溶かし、白土層を通過させ、
前駆物質を含まない目的物を得た。Both of the above crystals were combined and heated with an aqueous solution of sodium carbonate to precipitate p- (imidazolyl) as a crude product.
6.5 g of -2 ')-phenylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2") [hereinafter referred to as Z64A] was collected by filtration. This crude product may contain trace amounts of precursors.
Found by LC. Therefore, the crude product was dissolved in a mixed solution of methanol and methyl cellosolve and passed through a clay layer,
The target product containing no precursor was obtained.

【００４１】（実施例２）ｐ−（４'-メチルイミダゾリ
ニル-2')−フェニレン−〔4",6"-ジアミノ-1",3",5"-s-
トリアジン〕−(2")１０ｇ、塩基性炭酸銅２４．７ｇ、
無水炭酸ナトリウム３．５ｇ及びＤＭＦ３８mlの４者を
用いて、実施例１と同様の処理を行い、ｐ−（４'-メチ
ルイミダゾリル-2')−フェニレン−〔4",6"-ジアミノ-
1",3",5"-s-トリアジン〕−(2")〔以下、ＭＺ６４Ａと
いう〕７．４ｇを得た。Example 2 p- (4'-methylimidazolinyl-2 ')-phenylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-
Triazine]-(2 ") 10 g, basic copper carbonate 24.7 g,
The same treatment as in Example 1 was carried out by using 3.5 g of anhydrous sodium carbonate and 38 ml of DMF, and p- (4'-methylimidazolyl-2 ')-phenylene- [4 ", 6" -diamino-
There were obtained 7.4 g of 1 ", 3", 5 "-s-triazine]-(2") [hereinafter referred to as MZ64A].

【００４２】（実施例３）２−（イミダゾリニル-2')−
エチレン−（4",6"-ジアミノ-1",3",5"-s-トリアジン）
−(2")１０ｇ、塩基性炭酸銅１６．１ｇ、無水炭酸ナト
リウム３．６ｇ及びＤＭＦ３０mlの４者を、実施例１と
同様の方法により処理をして、２−（イミダゾリル-2')
−エチレン−（4",6"-ジアミノ-1",3",5"-s-トリアジ
ン）−(2")〔以下、Ｚ２Ａという〕６．０ｇを得た。(Example 3) 2- (imidazolinyl-2 ')-
Ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)
4- (2 ") 10 g, basic copper carbonate 16.1 g, anhydrous sodium carbonate 3.6 g and DMF 30 ml were treated in the same manner as in Example 1 to give 2- (imidazolyl-2 ').
There was obtained 6.0 g of -ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2") [hereinafter referred to as Z2A].

【００４３】（実施例４）２−（４'-メチルイミダゾリ
ニル-2')−エチレン−（4",6"-ジアミノ-1",3",5"-s-ト
リアジン）−(2")１０ｇ、塩基性炭酸銅２５．０ｇ、無
水炭酸ナトリウム３．５ｇ及びＤＭＦ５０mlの４者を、
実施例１と同様の方法により処理をして、２−（４'-メ
チルイミダゾリル-2')−エチレン−（4",6"-ジアミノ-
1",3",5"-s-トリアジン）−(2")〔以下、ＭＺ２Ａとい
う〕５．１ｇを得た。Example 4 2- (4'-Methylimidazolinyl-2 ')-ethylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2 ") 10 g, basic copper carbonate 25.0 g, anhydrous sodium carbonate 3.5 g and DMF 50 ml.
Treated in the same manner as in Example 1, 2- (4'-methylimidazolyl-2 ')-ethylene- (4 ", 6" -diamino-
5.1 g of 1 ", 3", 5 "-s-triazine)-(2") [hereinafter referred to as MZ2A] was obtained.

【００４４】（実施例５）２−（イミダゾリニル-2')−
ブチレン−（4",6"-ジアミノ-1",3",5"-s-トリアジン）
−(2")１０ｇ、硫酸銅５水塩２１．４ｇ、無水炭酸ナト
リウム１３．６ｇ及びＤＭＦ４０mlの４者を、実施例１
と同様の方法により処理をして、２−（イミダゾリル-
2')−ブチレン−（4",6"-ジアミノ-1",3",5"-s-トリア
ジン）−(2")〔以下、Ｚ４Ａという〕６．４ｇを得た。(Example 5) 2- (imidazolinyl-2 ')-
Butylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)
-(2 ") 10 g, copper sulfate pentahydrate 21.4 g, anhydrous sodium carbonate 13.6 g and DMF 40 ml were used in Example 1.
2- (imidazolyl-
There was obtained 6.4 g of 2 ')-butylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2") [hereinafter referred to as Z4A].

【００４５】（実施例６）２−（４'-メチルイミダゾリ
ニル-2')−ブチレン−（4",6"-ジアミノ-1",3",5"-s-ト
リアジン）−(2")１０ｇ、硫酸銅５水塩３０．０ｇ、無
水炭酸ナトリウム１７．０及びＤＭＦ４０mlの４者を、
実施例１と同様の方法により処理をして、２−（４'-メ
チルイミダゾリル-2')−ブチレン−（4",6"-ジアミノ-
1",3",5"-s-トリアジン）−(2")〔以下、ＭＺ４Ａとい
う〕４．９ｇを得た。(Example 6) 2- (4'-methylimidazolinyl-2 ')-butylene- (4 ", 6" -diamino-1 ", 3", 5 "-s-triazine)-(2 ") 10 g, copper sulfate pentahydrate 30.0 g, anhydrous sodium carbonate 17.0 and DMF 40 ml.
The same procedure as in Example 1 was carried out to give 2- (4'-methylimidazolyl-2 ')-butylene- (4 ", 6" -diamino-
Thus, 4.9 g of 1 ", 3", 5 "-s-triazine)-(2") [hereinafter referred to as MZ4A] was obtained.

【００４６】（実施例７）ｍ−（イミダゾリニル-2')−
フェニレン−〔4",6"-ジアミノ-1",3",5"-s-トリアジ
ン〕−(2")１０ｇ、塩化第二銅２水塩１０．３ｇ、無水
炭酸ナトリウム１２．５ｇ及びＤＭＦ３０mlの４者を、
実施例１と同様の方法により処理をして、ｍ−（イミダ
ゾリル-2')−フェニレン−〔4",6"-ジアミノ-1",3",5"-
s-トリアジン〕−(2")〔以下、Ｚ６３Ａという〕５．８
ｇを得た。Example 7 m- (imidazolinyl-2 ')-
Phenylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-triazine]-(2") 10g, cupric chloride dihydrate 10.3g, anhydrous sodium carbonate 12.5g and DMF 30ml. 4 of
Treated in the same manner as in Example 1, m- (imidazolyl-2 ')-phenylene- [4 ", 6" -diamino-1 ", 3", 5 "-
s-triazine]-(2 ") [hereinafter referred to as Z63A] 5.8
g was obtained.

【００４７】（実施例８）ｍ−（４'-メチルイミダゾリ
ニル-2')−フェニレン−〔4",6"-ジアミノ-1",3",5"-s-
トリアジン〕−(2")１０ｇ、塩化第二銅２水塩１４．６
ｇ、無水炭酸ナトリウム１５．８ｇ及びＤＭＦ３０mlの
４者を、実施例１と同様の方法により処理をして、ｍ−
（４'-メチルイミダゾリル-2')−フェニレン−〔4",6"-
ジアミノ-1",3",5"-s-トリアジン〕−(2")〔以下、ＭＺ
６３Ａという〕５．１ｇを得た。(Example 8) m- (4'-methylimidazolinyl-2 ')-phenylene- [4 ", 6" -diamino-1 ", 3", 5 "-s-
Triazine]-(2 ") 10 g, cupric chloride dihydrate 14.6
g, anhydrous sodium carbonate 15.8 g and DMF 30 ml were treated in the same manner as in Example 1 to give m-
(4'-Methylimidazolyl-2 ')-phenylene- [4 ", 6"-
Diamino-1 ", 3", 5 "-s-triazine]-(2") [hereinafter MZ
63A] 5.1 g was obtained.

【００４８】（実施例９）実施例１ないし８で得られた
イミダゾール環を有するジアミノ−ｓ−トリアジン化合
物を用いて１％溶液を調製した。その際に、Ｚ２Ａ、Ｍ
Ｚ２Ａ、Ｚ４Ａ及びＭＺ４Ａは水を用い、またＺ６３
Ａ、ＭＺ６３Ａ及びＺ６４Ａはメチルセロソルブを用
い、残りのＭＺ６４Ａはメタノールを用いて、それぞれ
１％溶液に調製した。一方、銅張積層板（幅２．５ｃ
ｍ、長さ７．０ｃｍ）を磨砂を用いて研磨し、これを試
験片とした。前記の各１％溶液を試験片の金属表面に濾
紙片を用いて塗布し、少時放置したのち、水洗乾燥し
た。これらの乾燥させた試験片を硫化水素が一日一回定
期的に少量発生する試験室内に３ケ月間放置した。放置
後の試験片を目視により観察したところ、、前記のイミ
ダゾール環を有するジアミノ−ｓ−トリアジン化合物を
含有する１％溶液を塗布した試験片は金属光沢を失って
いなかったが、１％溶液を塗布していない試験片は黒変
していた。Example 9 A 1% solution was prepared using the diamino-s-triazine compound having an imidazole ring obtained in Examples 1 to 8. At that time, Z2A, M
Z2A, Z4A and MZ4A use water and Z63
A, MZ63A and Z64A were prepared into 1% solutions by using methyl cellosolve and the remaining MZ64A by using methanol. On the other hand, copper clad laminate (width 2.5c
m, length 7.0 cm) was polished with sand and used as a test piece. Each of the above 1% solutions was applied to the metal surface of the test piece using a piece of filter paper, left for a short time, then washed with water and dried. These dried test pieces were left for 3 months in a test room where a small amount of hydrogen sulfide was regularly generated once a day. When the test piece after standing was visually observed, the test piece coated with the 1% solution containing the diamino-s-triazine compound having an imidazole ring did not lose the metallic luster, but the 1% solution was The uncoated test piece was blackened.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 化１の一般式で示されるイミダゾール環
を有するジアミノ−ｓ−トリアジン化合物。 【化１】 1. A diamino-s-triazine compound having an imidazole ring represented by the general formula of Chemical formula 1. [Chemical 1] 【請求項２】 化１の一般式で示されるイミダゾール環
を有するジアミノ−ｓ−トリアジン化合物を含む溶液を
銅あるいは銅合金の表面に接触させることを特徴とする
銅の防錆方法。2. A method of preventing rusting of copper, which comprises bringing a solution containing a diamino-s-triazine compound having an imidazole ring represented by the general formula of Chemical Formula 1 into contact with the surface of copper or a copper alloy.
JP5202584A 1993-07-23 1993-07-23 Diamino-s-triazine compound having imidazole ring and method for preventing copper from rusting using the same compound Pending JPH0733766A (en)

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JPH0733766A true JPH0733766A (en) 1995-02-03

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