JPS6112675A - Pyrimidine derivative - Google Patents
Pyrimidine derivativeInfo
- Publication number
- JPS6112675A JPS6112675A JP59133501A JP13350184A JPS6112675A JP S6112675 A JPS6112675 A JP S6112675A JP 59133501 A JP59133501 A JP 59133501A JP 13350184 A JP13350184 A JP 13350184A JP S6112675 A JPS6112675 A JP S6112675A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- pyrimidine
- reaction
- tetradecyl
- 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
Links
- 150000003230 pyrimidines Chemical class 0.000 title claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- 238000010992 reflux Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 2
- 150000003937 benzamidines Chemical class 0.000 abstract description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 abstract description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 abstract 1
- 238000010511 deprotection reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 230000002140 halogenating effect Effects 0.000 abstract 1
- 239000012442 inert solvent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- -1 alkyl malonate Chemical compound 0.000 description 8
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical class C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- MRCBGFDKDHZDCD-UHFFFAOYSA-N 4-(5-nonylpyrimidin-2-yl)phenol Chemical compound N1=CC(CCCCCCCCC)=CN=C1C1=CC=C(O)C=C1 MRCBGFDKDHZDCD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000023320 Luma <angiosperm> Species 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium on carbon Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 102100023185 Transcriptional repressor scratch 1 Human genes 0.000 description 1
- 101710171414 Transcriptional repressor scratch 1 Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LZCZIHQBSCVGRD-UHFFFAOYSA-N benzenecarboximidamide;hydron;chloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=C1 LZCZIHQBSCVGRD-UHFFFAOYSA-N 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- GESHRHVYCSRGQP-UHFFFAOYSA-N diethyl 2-tetradecylpropanedioate Chemical compound CCCCCCCCCCCCCCC(C(=O)OCC)C(=O)OCC GESHRHVYCSRGQP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はピリミジン誘導体に関するものであ〔式中ｎは
９〜１４の整数を示す。〕
で示される新規ピリミジン誘導体に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pyrimidine derivatives, where n represents an integer of 9 to 14. ] This relates to a novel pyrimidine derivative represented by the following.
大田で示される化合物は液晶化合物の製造原ネ１として
有用な化合物である。The compound shown by Ohta is a compound useful as a raw material 1 for producing liquid crystal compounds.
従来、７本発明の目的化合物の同族化合物にっいて報告
がなされている（例えば、東ドイツ特許第１４４４０９
号）が、本発明者らによって提供されるような倒錯に炭
素数の多いアルキル基を置換基として有する成田で示さ
れるピリミジン誘導体はまだ知られていない。本発明は
かかる新規な化合物を提供するものである。So far, seven homologues of the target compound of the present invention have been reported (for example, East German Patent No. 144409).
The pyrimidine derivatives shown in Narita having a perverted alkyl group with a large number of carbon atoms as a substituent as provided by the present inventors are not yet known. The present invention provides such novel compounds.
炭素数の多いアルキル基を置換基として持っていること
による本発明目的化合物の特性は今後の研究によってさ
らに明らかにされるのであろうが、本発明目的化合物を
原料として液晶化合物をつくった場合、置換基としての
アルキル基の炭素数の大きさが、液晶性を示す温度範囲
、応答スピードなどの改善、他の液晶化合物との混和性
に効果的に関係するのではないかと期待される。The properties of the compounds of the present invention due to having an alkyl group with a large number of carbon atoms as a substituent will be further clarified through future research, but when a liquid crystal compound is made from the compound of the present invention as a raw material, It is expected that the number of carbon atoms in the alkyl group as a substituent is effectively related to the temperature range in which liquid crystallinity is exhibited, improvement in response speed, etc., and miscibility with other liquid crystal compounds.
本発明の目的化合物はそれ自体公知の方法に準じてつく
ることもできるが、例えば、次のような合成式で製造す
ることができる。Although the target compound of the present invention can be produced according to a method known per se, for example, it can be produced according to the following synthetic formula.
〔式中Ｒ１け水素原子、ベンジル基、アリル基またはピ
ラニル基を、Ｒ２はＯｎ Ｈ２’ｎ ＋１１ ｎは９〜
１４の整数）を、馬は低級アルキル基を、Ｘはハロゲン
原子を示す◇〕
ここにおいて、式〔ヨ〕で示されるベンズアミジン誘導
体の塩酸ｊｆｆｌと式（１）で示されるアルキルキルマ
ロン酸シアキルエステルとから、式（ＩＶ）で示される
化合物を得る反応はアルコラード又はアルカリ金属の存
在下に行なわれ、゛反応に関与しない溶媒、たとえばメ
タノール、エタノールナトのアルコール類、ベンゼン、
トルエン、ＤＭＳｏｌＤＭＦなどを適宜に使用すること
ができる。反応は還流下に行うのがよい。[In the formula, R1 is a hydrogen atom, benzyl group, allyl group or pyranyl group, R2 is On H2'n +11 n is 9 to
(an integer of 14), horse represents a lower alkyl group, and X represents a halogen atom◇] Here, jffl hydrochloride of a benzamidine derivative represented by the formula [Y] and siakyl alkyl malonate represented by the formula (1) The reaction to obtain the compound represented by formula (IV) from the ester is carried out in the presence of an alcoholade or an alkali metal, and a solvent that does not participate in the reaction, such as methanol, alcohols such as ethanol, benzene,
Toluene, DMSoIDMF, etc. can be used as appropriate. The reaction is preferably carried out under reflux.
次に、式（■〕で示される化合物を得るにけ式（１’Ｖ
）で示される化合物と、オキシハロゲン化リン、三又は
五ハロゲン化リンなどの・・ロケン化剤とを触媒の存在
で還流下に反応させる。用いられる触媒としてはＮ、Ｎ
−ジエチルアニリン、ピリジンなどの塩基性触５媒があ
げられるが、Ｎ１Ｎ−ジエチルアニリンが好ましい。Next, to obtain a compound represented by the formula (■), the formula (1'V
) is reacted with a rokenizing agent such as phosphorus oxyhalide, phosphorus trihalide, or phosphorus pentahalide under reflux in the presence of a catalyst. The catalysts used are N, N
Examples include basic catalysts such as -diethylaniline and pyridine, with N1N-diethylaniline being preferred.
次いで、式（Ｖ）で示される化合物を接触還元すること
によって保護基の脱離、脱ハロゲン化水素が同時に行な
われ、式ＣＩ）で示される化合物が得られる。Next, the compound represented by formula (V) is subjected to catalytic reduction to simultaneously remove the protecting group and dehydrohalogenate, thereby obtaining the compound represented by formula CI).
一方、式０〕で示される化合物と式（Ｖｌ）で示される
アクロレイン誘導体との反応は、アルコラード又はアル
カリ金属の存在下にメタノール、エタノールナトのアル
コール類、又はベンゼン、トルエンなどの芳香族炭化水
素系溶媒中で還流下に行なわれて式（■〕（Ｒ１が水素
のときは式（Ｉ））で示される化合物を得、接触還元を
行うか、ま′には、塩酸、臭化水素酸なとの鉱酸、もし
くけＡＩ Ｃ１３、ＺｎＣｌ２などのルイス酸で処理
することによｐ１式ＣＩ）で示される化合物を得ること
ができる。On the other hand, the reaction between the compound represented by formula 0] and the acrolein derivative represented by formula (Vl) can be carried out using alcohols such as methanol or ethanolate, or aromatic hydrocarbons such as benzene or toluene in the presence of alcoholade or an alkali metal. The reaction is carried out under reflux in a system solvent to obtain a compound represented by formula (■) (formula (I) when R1 is hydrogen), and catalytic reduction is carried out, or alternatively, hydrochloric acid, hydrobromic acid A compound of formula p1 (CI) can be obtained by treatment with a Lewis acid such as Nato mineral acid, Moshike AI C13, ZnCl2, etc.
以下１１本発明を具体的に説明中るだめ実施例を記述す
る。Below, eleven embodiments will be described to specifically explain the present invention.
実施例１゜
Ａ）５−ｎ−テトラデシＸルー２−（４−ベンジルオキ
シフェニル） −４，６−ジヒドロ゛キシピリミジンの
製造：
５００ｍ１の四ソロフラスコに、金属ナトリウム１４．
４８ｇ、乾燥メタ／−に８８０ｍ１を入れ、ナトリウム
メチラート・メタノール溶液をつくった。この溶液に４
−ペンジルオキンペンズアミジン塩酸塩５０ｇ、次いで
、ｎ−テトラデシルマロン酸ジエチルエステル６．７．
８５ｆを入れ、加熱還流下にＪ３時間反応した。冷却後
、硫酸にて酸性とし、結晶を析出させた。結晶をＰ側抜
、精製し、５−ｎ−テトラデシル−２−（４−ベンジル
オキシフェニルＩ−４，６−シヒドロキシビリミジン９
０ｇを得た。Example 1 A) Preparation of 5-n-tetradecyX-2-(4-benzyloxyphenyl)-4,6-dihydroxypyrimidine: In a 500 ml tetrasol flask, 14.
48 g of dry meth/- was added to 880 ml to prepare a sodium methylate/methanol solution. Add 4 to this solution
- 50 g of penzyloquinpenzamidine hydrochloride, then 6.7 g of n-tetradecylmalonic acid diethyl ester.
85f was added thereto, and the reaction was carried out for J3 hours under heating and reflux. After cooling, the mixture was made acidic with sulfuric acid to precipitate crystals. The crystals were extracted from the P side and purified to give 5-n-tetradecyl-2-(4-benzyloxyphenyl I-4,6-cyhydroxypyrimidine 9
Obtained 0g.
Ｉ−Ｂ・（Ｎｕｊｏｌ） Ｑ＝ａ６ｏｏ−２０００ｃ
Ｍ−１Ｂｌ ’ ５− ｎ−テトラデシル−２−（４−
ベンジルオキシフェニル１−４．６−ジクロロピリミジ
ンの製造：
１０００Ｑの７ ラスニア Ｋ、５−ｎ−ｆトラデシル
−２−（４−ベンジルオキシフェニル） −４，６−シ
ヒドロキシピリミジン８５ｇ、オキシ塩化り７４２５ｍ
１ＳＮ、 Ｎ −ジエチルアニリン６４ｍを入れ、加熱
還流下に２２時間反応した。反応後、過剰ノオキシ塩化
リンを留去し１、残渣を氷水に注いだ。酢酸エチルにて
抽出シ２、アルカリ水溶液、水、飽和食塩水で洗浄した
。酢酸エチル層を乾燥後、酢酸エチルを留去し、粗生成
物を得た。これを精製し５て、５−ｎ−テトラデシル−
２−（４−ペンジルオキンフ工二ル） −４，６−ジク
ロロピリミジン４３ｙを得た。I-B・(Nujol) Q=a6oo-2000c
M-1Bl' 5- n-tetradecyl-2-(4-
Production of benzyloxyphenyl 1-4,6-dichloropyrimidine: 1000Q of 7 Lasnia K, 5-n-f tradecyl-2-(4-benzyloxyphenyl)-4,6-cyhydroxypyrimidine 85g, oxychloride 7425m
64 m of 1SN, N-diethylaniline was added, and the mixture was reacted under heating under reflux for 22 hours. After the reaction, excess nooxyphosphorus chloride was distilled off (1), and the residue was poured into ice water. It was extracted with ethyl acetate and washed with an aqueous alkaline solution, water, and saturated brine. After drying the ethyl acetate layer, ethyl acetate was distilled off to obtain a crude product. This was purified and 5-n-tetradecyl-
2-(4-Penzyl)-4,6-dichloropyrimidine 43y was obtained.
ＩＲ（Ｎｕｊｏｌ ）
Ｑ＝１６ｔｏ、１２５’５ ｆｆ−１
”Ｈ−ＮＭＲ（６０ＭＨｚ、ＣＤＣＩＣＤＣｌ５ｒ（ｐ
ｐ、ａ５（ａ、２ｌ−１）７．０２ｆｄ、２Ｈ）
７．２５−７．６０ （ｍ、 ５Ｈ）
５．０９（８，２Ｈ）
２．８５（ｔ、２）（）
ｍ−ｐ−７１−７２，５Ｃ
（１）５−ｎ−テトラデシル−２−（４−ヒドロキンフ
ェニル）ピリミジンの製造。IR (Nujol) Q=16to, 125'5 ff-1"H-NMR (60MHz, CDCICDCl5r(p
p, a5 (a, 2l-1) 7.02fd, 2H) 7.25-7.60 (m, 5H) 5.09 (8, 2H) 2.85 (t, 2) () m-p- 71-72,5C (1) Production of 5-n-tetradecyl-2-(4-hydroquinphenyl)pyrimidine.
１０１００Ｏ！のフラスコに、５−ｎ−ｆトラテンルー
２−１４−ベンジルオキ７フエニル）−４，６−ジクロ
ロピリミジン２３ｇ、１０％Ｐｄ／Ｃ４，６ｇ、酸化マ
グネシウム６．８９ｇ、エタノール７１８ｍ１．水６３
ｍ１を入れ、理論量の水素を吸収するまで水素添加し５
た。反応後、触媒を炉別し２、エタノールを留去後、希
塩酸を加えて酸性とした。10100O! 23 g of 5-n-ftraten-2-14-benzylox7phenyl)-4,6-dichloropyrimidine, 4.6 g of 10% Pd/C, 6.89 g of magnesium oxide, and 718 ml of ethanol. water 63
ml and hydrogenate until the theoretical amount of hydrogen is absorbed.
Ta. After the reaction, the catalyst was separated from the furnace 2, and after ethanol was distilled off, dilute hydrochloric acid was added to make it acidic.
次いで酢酸エチルにて抽出し、水、飽和食塩水で洗浄し
、乾燥し７たのち、酢酸エチルを留去し、粗生成物を得
だ。これを精製して、５、− ｎ−テトラデシル−２〜
（４−ヒドロキンフェニル）ピリミジン１２Ｍを得た。Next, the mixture was extracted with ethyl acetate, washed with water and saturated brine, dried, and then ethyl acetate was distilled off to obtain a crude product. This was purified to give 5,-n-tetradecyl-2~
12M of (4-hydroquinphenyl)pyrimidine was obtained.
ｍ−ｐ−６８〜６５Ｃ
実施例２゜
実施例１と同様の方法にて５−ｎ−ウンデシル−２１４
−ヒドロキシフェニル）ヒリジンを得た。m-p-68-65C Example 2゜5-n-undecyl-214 in the same manner as Example 1
-hydroxyphenyl)hyridine was obtained.
実施例３゜
Ａｌ −５−ｎ−テトラデシル−２−（４−ヒドロギン
フェニル）−４，６−シヒドロキシピリミジンの製造：
２００ｍ１のナスフラスコに４−ヒドロキノベンズアミ
ジン塩酸塩１０ｇ、ｎ−ナト３七ルマＯｄｅジエチルエ
ステル２０．７９を入れ、、乾燥エタノール５０ｍ１を
加えて懸濁させ、さらに、２８％ナトリウムメチラート
溶液を加えて還流下に１４時間反応した。反応液を氷水
に注ぎ、希塩酸で酸性とし、析出する結晶を瀘取して、
５−ｎ−テトラゾフルー２−（４−ヒドロキンフェニル
）ピリミジン２３．１９を得た。Example 3 Production of Al-5-n-tetradecyl-2-(4-hydroginphenyl)-4,6-cyhydroxypyrimidine: In a 200 ml eggplant flask, 10 g of 4-hydroquinobenzamidine hydrochloride, n-nato 20.79 of 37 luma Ode diethyl ester was added thereto, 50 ml of dry ethanol was added to suspend the mixture, and a 28% sodium methylate solution was added thereto and the mixture was reacted under reflux for 14 hours. The reaction solution was poured into ice water, made acidic with dilute hydrochloric acid, and the precipitated crystals were filtered.
23.19 of 5-n-tetrazofluor-2-(4-hydroquinphenyl)pyrimidine was obtained.
ＩＲ（Ｎｕｊｏｌ ）
９＝ａ６ｏｏ〜２０００．１６０５．１５００α−１Ｂ
）５−ｎ−テトラデシル−２−（４−ヒドロキンフェニ
ル）−４，６−ジクロロピリミジンの製造：
２００ｍ１のナス’７ ラスコに、５−ｎ−７トラテシ
ルー２− ’Ｉ ４−ヒドロキシフェニル）＝ ４．６
−シヒドロキシピリミジン２０ｇを入れ、オキシ塩化リ
ン１００ｍ１及びＮ１Ｎ−ジエチルアニリン１５ｍ１を
加えて、還流下に１２時間反応した。反応後、過剰のオ
キシ塩化リンを留去し、残渣を氷水に注いだ。IR (Nujol) 9=a6oo~2000.1605.1500α-1B
) Preparation of 5-n-tetradecyl-2-(4-hydroquinphenyl)-4,6-dichloropyrimidine: In a 200 ml eggplant '7 lasco, add 5-n-7tratecyl-2-(4-hydroxyphenyl)= 4.6
20 g of -cyhydroxypyrimidine was added, 100 ml of phosphorus oxychloride and 15 ml of N1N-diethylaniline were added, and the mixture was reacted under reflux for 12 hours. After the reaction, excess phosphorus oxychloride was distilled off, and the residue was poured into ice water.
酢酸エチルにて抽出し、水、飽和食塩水で洗浄後、乾燥
し、酢酸エチルを留去し、粗生成物を得た。これをシリ
カゲルクロマトにて精製して５−テトラデシル−２−（
４−ヒドロキシフェニル）−４，６−シクロロビ１）ミ
ジン２７ｆを得た０
ＩＦ（Ｎｕｊｏｌ ）））＝１６００．１５５０．１４
００傷−１
Ｎ ＭＲ（６０ＭＨｚ、 ＣＤＣｌ５）、Ｊ（ｐｐｍ
）＝８．２４ （ｄ、２Ｈ，） ６．８５（ｄ、２Ｈ
）Ｇ）５−ｎ−テトラデシル−２−（４−ヒドロキシフ
ェニル）ピリミジンの製造：
５−ｎ−テトラデシル−２−（４−ヒドロキシフェニル
）−４，６−ジクロロピリミジン１５ｇをエタ／ ／
ｌ／４８０ｍ１％水４０ｍ１ｋＣ溶かし、これに１０％
ｐｄ７ｃ ｓ、５ｙ及び酸化マグネンウム５．４ｇを
加えて、理論量の水素を吸収するまで水素添加した。The extract was extracted with ethyl acetate, washed with water and saturated brine, and dried. Ethyl acetate was distilled off to obtain a crude product. This was purified using silica gel chromatography and 5-tetradecyl-2-(
4-Hydroxyphenyl)-4,6-cyclobi1) Midine 27f was obtained 0 IF(Nujol))) = 1600.1550.14
00 scratch-1 N MR (60MHz, CDCl5), J (ppm
) = 8.24 (d, 2H,) 6.85 (d, 2H
) G) Production of 5-n-tetradecyl-2-(4-hydroxyphenyl)pyrimidine: 15 g of 5-n-tetradecyl-2-(4-hydroxyphenyl)-4,6-dichloropyrimidine was added to ether/ /
Dissolve l/480ml 1% water 40ml 1kC, add 10%
pd7cs,5y and 5.4 g of magnesium oxide were added and hydrogenated until the theoretical amount of hydrogen was absorbed.
反応終了後、触媒を戸別し、溶媒を留去後、希塩酸を加
えて酸性とした。次いで酢酸エチルにて抽出し７、水、
飽和食塩水で洗浄し、乾Ｓ Ｌ、たのも、酢酸エチルを
留去し、て粗生成物を得た。After the reaction was completed, the catalyst was separated and the solvent was distilled off, followed by addition of dilute hydrochloric acid to make it acidic. Then extracted with ethyl acetate 7, water,
The mixture was washed with saturated brine, dried with SL, and ethyl acetate was distilled off to obtain a crude product.
このものをｎ−へキサンと少量のエーテルよシ晶析Ｌ−
、Ｐ取して５−ｎ−テトラゾツルー２−（４−ヒドロキ
ンフェニル）ビ１１ミジン８８ｇを得た。Crystallize this product with n-hexane and a small amount of ether.
, P was removed to obtain 88 g of 5-n-tetrazotrue-2-(4-hydroquinphenyl)bi-11midine.
実施例４゜
５−ｎ−ノニル−２−（４−ヒドロキシフェニル）ピリ
ミジンの製造：
５０ｍ１のフラスコに４−ヒドロキンベンズアミジン塩
酸塩１．５ｇ、α−ｎ−ノニル−β−ジメチルアミンア
クロレイン１．９６１、乾燥メタノール１５ｍ１を入れ
た。この混合物に、水冷下、金属ナトリウムと乾燥メタ
ノールより調整したナト１１ウムメチラート・メタノー
ル溶液をゆっくりと滴下し、還流下８時間反応した。反
応終了後、アルコールを留去し、残渣を氷水に注ぎ、酸
性としたのち、酢酸エチルで抽出した。Example 4 Preparation of 5-n-nonyl-2-(4-hydroxyphenyl)pyrimidine: 1.5 g of 4-hydroquine benzamidine hydrochloride, α-n-nonyl-β-dimethylamine acrolein 1 in a 50 ml flask. .961, and 15 ml of dry methanol was added. To this mixture was slowly added dropwise a methanol solution of sodium 11ium methylate prepared from sodium metal and dry methanol under water cooling, and the mixture was reacted under reflux for 8 hours. After the reaction was completed, the alcohol was distilled off, the residue was poured into ice water to make it acidic, and then extracted with ethyl acetate.
酢酸エチル層を水、飽和食塩水で洗浄後、乾燥し、溶媒
を留去した。得た粗生成物を精製して５−ｎ−／ニルー
２−（４−ヒドロキンフェニル）ピリミジン１．９ｇを
得た。The ethyl acetate layer was washed with water and saturated brine, dried, and the solvent was distilled off. The obtained crude product was purified to obtain 1.9 g of 5-n-/ni-2-(4-hydroquinphenyl)pyrimidine.
実施例５・６・７
実施例４と同様の方法にて５−ｎ−デンルー２−（４−
ヒドロキンフェニル）ピリミジン、５・ｎ−ドデシル−
２１４−ヒドロキシラエニル）ピリミジン、５−ｎ〜ト
リデシル−２−（４−ヒドロキシフェニル）ピリミジン
？ （４ｆｊ ｆｔ＝。Examples 5, 6, and 7 5-n-Denru 2-(4-
Hydroquinphenyl)pyrimidine, 5・n-dodecyl-
214-hydroxylaenyl)pyrimidine, 5-n~tridecyl-2-(4-hydroxyphenyl)pyrimidine? (4fj ft=.
実施例８゜
Ａ）５＝ｎ−デシル−２−（４−ベンジルオキシフェニ
ル）ピ１１ミジンの製造：
８ｏｍｉのフラスコに４−ペンジルオキンペンズアミジ
ン塩酸塩２．０７ Ｆｌ 、α−ｎ−７’ シ／ｌ／−
β−ジメチルアミンアクロレイン］、、 ’８８９ 、
乾燥エタノール２０．ｒｎｌを入れた。Example 8゜A) Preparation of 5=n-decyl-2-(4-benzyloxyphenyl)pi11midine: In an 8omi flask, 2.07 Fl of 4-penzyloxinpenzamidine hydrochloride, α-n- 7' shi/l/-
β-dimethylamine acrolein], '889,
Dry ethanol20. I added rnl.
この混合物に、氷冷下、金属ナト１７ウム０゜７２ｇど
乾燥エタノールより調整したナトリウムエチラート・エ
タノール溶液をゆっ、くり滴下して加えた後、還流下に
７時間反応した。反応終了後、エタノールを留去し、残
渣を酢酸エチルで抽出した。酢酸エチル層を水、飽和食
塩水で洗浄し、乾燥後、溶媒を留去し、粗生成物を得た
。これを精製して５−ｎ−デシル−２−（４−ベンジル
オキシフェニル）ピリミジン２．３７ｇ１ｌｋ。To this mixture was slowly added dropwise a solution of sodium ethylate in ethanol prepared from dry ethanol containing 0.72 g of sodium metal under ice-cooling, and the mixture was reacted under reflux for 7 hours. After the reaction was completed, ethanol was distilled off, and the residue was extracted with ethyl acetate. The ethyl acetate layer was washed with water and saturated brine, dried, and then the solvent was distilled off to obtain a crude product. This was purified to yield 2.37 g/lk of 5-n-decyl-2-(4-benzyloxyphenyl)pyrimidine.
ＩＲ（Ｎｕｊｏｌ）
９−１６１０．１５８５．１２５０ｃＭ ”７Ｈ−ＮＭ
Ｒ（６０ＭＨｚ、 ＣＤＣＩＣＤＣｌ５）ｆ（ｐｐ、５
６ｔｓ、２Ｈ）
８．４０ （ｄ、 ２Ｉ（）
７．０５（（１，２）Ｔ１
７．３−７．６ （ｔｎ、 ５Ｈ）
５、’Ｉ Ｏ（ｓ、 ２Ｈ）
Ｂ）５−ｎ−デシル−２−（４−ヒドロキシフェニル）
ピリミジンの製造：
５Ｑｍ６のフラスコに５−ｎ−デシル−２−（４−ベン
ジルオキシフェニル）ピリミジン０．５８ ｆ／、１０
％Ｐｄ／Ｇ Ｏ，５９、エタノール１５ｍ１Ｖを入れ
、理論量の水素が吸収されるまで水素添加Ｌ〜だ。IR (Nujol) 9-1610.1585.1250cM "7H-NM
R(60MHz, CDCICDCl5)f(pp, 5
6ts, 2H) 8.40 (d, 2I() 7.05((1,2)T1 7.3-7.6 (tn, 5H) 5,'IO(s, 2H) B) 5-n -decyl-2-(4-hydroxyphenyl)
Preparation of pyrimidine: 5-n-decyl-2-(4-benzyloxyphenyl)pyrimidine 0.58 f/, 10 in a 5Qm6 flask
% Pd/G O, 59, and 15 mL of ethanol were added, and hydrogenation was continued until the theoretical amount of hydrogen was absorbed.
反応終了−後、触媒を炉別し５、エタノールを留去した
。得た粗生成物を精製し、て５−ｎ−テシルー２−（４
−ヒドロキシフェニルピリミジン０．４９を得た。After the reaction was completed, the catalyst was removed from the furnace 5, and ethanol was distilled off. The obtained crude product was purified to give 5-n-tesilyl-2-(4
-Hydroxyphenylpyrimidine 0.49 was obtained.
実が６例で得た化合物の物性値を表１にまとめて記す。The physical properties of the compounds obtained in six cases are summarized in Table 1.
表中の数字は次の条件で測定し７だ値を示す。The numbers in the table indicate the values measured under the following conditions.
ＩＦｔは流動パラフィンと試料と混合して測定Ｏ
”）（−ＮＭＲけ重クロロホルム中、５０ＭＨ：を用い
て測定。IFt is measured by mixing liquid paraffin with the sample.
（↓
手続補正書（方式）
％式％
１、 事件の表示
昭和５９年特許願第１３３５ｏ１号
２ 発明の名称
ピ謁ブン誘導体
３ 補正をする者
事件との関係 特許出願人
住 所 大阪市西区北堀江１丁目１番１８号４ 補正命
令の日付
昭和５９年９月２５日（発送日）
５、補正の対象
１）願 書
２）明細書
６ 補正の内容(↓ Procedural amendment (method) % formula % 1, Indication of the case 1982 Patent Application No. 1335o1 2 Name of the invention Pi-audience derivative 3 Relationship with the person making the amendment Patent applicant address Kita, Nishi-ku, Osaka 1-18 Horie 1-chome 4 Date of amendment order September 25, 1980 (shipment date) 5. Subject of amendment 1) Application 2) Description 6 Contents of amendment
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59133501A JPS6112675A (en) | 1984-06-27 | 1984-06-27 | Pyrimidine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59133501A JPS6112675A (en) | 1984-06-27 | 1984-06-27 | Pyrimidine derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6112675A true JPS6112675A (en) | 1986-01-21 |
Family
ID=15106242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59133501A Pending JPS6112675A (en) | 1984-06-27 | 1984-06-27 | Pyrimidine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6112675A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61189274A (en) * | 1985-02-15 | 1986-08-22 | Teikoku Chem Ind Corp Ltd | Phenylpyrimidine derivative |
| JPH0466087A (en) * | 1990-07-05 | 1992-03-02 | Sunstar Inc | Method for stabilizing ascorbate oxidase and stabilized composition of the same enzyme |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5653661A (en) * | 1979-08-20 | 1981-05-13 | Ueruku Fuyuuru Fuerunzeeerekut | Nematic crystal liquid 55alkyll22*44acyloxyy phenyl**pyrimidine* its manufacture and its use |
| JPS5793934A (en) * | 1980-09-29 | 1982-06-11 | Werk Fernsehelektronik Veb | Liquid crystal substance and manufacture |
| JPS60255779A (en) * | 1984-05-31 | 1985-12-17 | Chisso Corp | Heterocyclic compound |
-
1984
- 1984-06-27 JP JP59133501A patent/JPS6112675A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5653661A (en) * | 1979-08-20 | 1981-05-13 | Ueruku Fuyuuru Fuerunzeeerekut | Nematic crystal liquid 55alkyll22*44acyloxyy phenyl**pyrimidine* its manufacture and its use |
| JPS5793934A (en) * | 1980-09-29 | 1982-06-11 | Werk Fernsehelektronik Veb | Liquid crystal substance and manufacture |
| JPS60255779A (en) * | 1984-05-31 | 1985-12-17 | Chisso Corp | Heterocyclic compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61189274A (en) * | 1985-02-15 | 1986-08-22 | Teikoku Chem Ind Corp Ltd | Phenylpyrimidine derivative |
| JPH0466087A (en) * | 1990-07-05 | 1992-03-02 | Sunstar Inc | Method for stabilizing ascorbate oxidase and stabilized composition of the same enzyme |
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