JPS63145254A - Naphthoic acid derivative - Google Patents
Naphthoic acid derivativeInfo
- Publication number
- JPS63145254A JPS63145254A JP29457386A JP29457386A JPS63145254A JP S63145254 A JPS63145254 A JP S63145254A JP 29457386 A JP29457386 A JP 29457386A JP 29457386 A JP29457386 A JP 29457386A JP S63145254 A JPS63145254 A JP S63145254A
- Authority
- JP
- Japan
- Prior art keywords
- naphthoic acid
- hydroxy
- amount
- sulfuric acid
- reaction
- 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
- 150000005209 naphthoic acids Chemical class 0.000 title 1
- WKZWCYSBCPVEKB-UHFFFAOYSA-N 7-tert-butyl-1-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC(C(O)=O)=C(O)C2=CC(C(C)(C)C)=CC=C21 WKZWCYSBCPVEKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 24
- -1 1-hydroxy-2-naphthoic acid ester Chemical class 0.000 abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229940121375 antifungal agent Drugs 0.000 abstract description 3
- 239000003429 antifungal agent Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 241000228212 Aspergillus Species 0.000 abstract description 2
- 241000221955 Chaetomium Species 0.000 abstract description 2
- 230000000843 anti-fungal effect Effects 0.000 abstract description 2
- 239000003317 industrial substance Substances 0.000 abstract description 2
- 241000222290 Cladosporium Species 0.000 abstract 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 1
- 241000233866 Fungi Species 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- FRSSDDRBJHZBBM-UHFFFAOYSA-N C(CCC)C=1C(=C(C2=CC=CC=C2C1)O)C(=O)O Chemical group C(CCC)C=1C(=C(C2=CC=CC=C2C1)O)C(=O)O FRSSDDRBJHZBBM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- HMIBDRSTVGFJPB-UHFFFAOYSA-N methyl 1-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC=CC2=C(O)C(C(=O)OC)=CC=C21 HMIBDRSTVGFJPB-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は工業上有用な新規化合物に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to novel compounds that are industrially useful.
ｌ−ヒドロキシ−２−ナフトエ酸が染料合成中間体、顕
色型分散染料などとして使われていることは広く知られ
ている。It is widely known that l-hydroxy-2-naphthoic acid is used as a dye synthesis intermediate, a color-developing disperse dye, and the like.
本発明者らは工業上有用なナフトエ酸＝ｉ体を開発する
ことを目的として種々検討を行なった。The present inventors conducted various studies with the aim of developing an industrially useful naphthoic acid i-form.
その結果、本発明者らは第３級ブチル基で置換された新
規なナフトエ酸化合物が工業上有用であることを見出し
、本発明を完成させた。すなわち、本発明は式
で表わされる７−第３級ブチル−１−ヒドロキシ−２−
ナフトエ酸に関する。As a result, the present inventors discovered that a novel naphthoic acid compound substituted with a tertiary butyl group is industrially useful, and completed the present invention. That is, the present invention provides 7-tert-butyl-1-hydroxy-2-
Concerning naphthoic acid.
本発明化合物である７−第３級ブチル−１−ヒドロキシ
−２−ナフトエ酸は、１−ヒドロキシ−２−ナフトエ酸
エステルと第３級ブチル化剤とをフリーゾルタラフッ反
応に付し、その後、加水分解することにより製造される
。7-tertiary butyl-1-hydroxy-2-naphthoic acid, which is a compound of the present invention, is obtained by subjecting 1-hydroxy-2-naphthoic acid ester and a tertiary butylating agent to a free-sol fluoride reaction, and then , produced by hydrolysis.
第３級ブチル化剤としては、第３級ブタノール、イソブ
タノール、イソブチレンなどが、フリーゾルタラフッ反
応に用いられる触媒としては、硫酸、リン酸、塩酸、フ
ッ化水素などのプロトン酸、塩化アルミニウム、五塩化
アンチモン、塩化第二鉄、四塩化スズ、四塩化チタンな
どのルイス酸などがあげられる。Tertiary butylating agents include tertiary butanol, isobutanol, isobutylene, etc. Catalysts used in free-sol fluoride reactions include protonic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and hydrogen fluoride, and aluminum chloride. , Lewis acids such as antimony pentachloride, ferric chloride, tin tetrachloride, and titanium tetrachloride.
本発明の化合物を製造する場合、フリーデルクラフッ触
媒としてはプロトン酸が好ましく、特に取扱いや廃酸処
理の容易さを考慮すると、硫酸を使用するのが工業上有
利である。この場合、原料のナフトエ酸化合物に対し、
硫酸を５重量倍以上使用すると、目的物が高収率で得ら
れる。When producing the compound of the present invention, a protonic acid is preferable as the Friedelkraff catalyst, and it is industrially advantageous to use sulfuric acid, especially considering ease of handling and waste acid treatment. In this case, for the raw naphthoic acid compound,
When sulfuric acid is used in an amount of 5 times or more by weight, the desired product can be obtained in high yield.
しかしながら、経済性のみならず廃硫酸の処理など環境
保全の立場からも硫酸の使用量を減らすことが望まれる
。しかるに、出発原料および目的化合物のナフトエ酸化
合物はともに硫酸にほとんど溶けないため、硫酸の使用
量を少なくすると攪拌不十分となり、反応試剤の接触が
妨げられ反応率が大幅に低下することになる。However, it is desirable to reduce the amount of sulfuric acid used not only from an economic standpoint but also from the standpoint of environmental protection such as disposal of waste sulfuric acid. However, since both the starting material and the target compound, the naphthoic acid compound, are hardly soluble in sulfuric acid, reducing the amount of sulfuric acid used will result in insufficient stirring, which will prevent contact between the reaction reagents and significantly reduce the reaction rate.
本発明者らは、反応希釈剤として芳香族炭化水素、エス
テル、ケトン、エーテル、有機酸、ジメチルホルムアミ
ド、ジメチルスルホキシドなどの各種溶媒類を広範囲に
亙って、その効果を探索した。その結果、スルホン化な
どの副反応を著しく促進する溶媒もある中で、脂肪族飽
和炭化水素または芳香族炭化水素を少量添加して反応す
ると、硫酸使用量を大幅に減少した場合でも、高収率で
目的物が得られることを見出した。The present inventors investigated the effects of a wide range of solvents such as aromatic hydrocarbons, esters, ketones, ethers, organic acids, dimethylformamide, and dimethyl sulfoxide as reaction diluents. As a result, while some solvents can significantly accelerate side reactions such as sulfonation, it has been found that when a small amount of aliphatic saturated hydrocarbon or aromatic hydrocarbon is added to the reaction, the yield is high even when the amount of sulfuric acid used is significantly reduced. It was found that the desired product could be obtained at a relatively low rate.
以下、この方法をより具体的に説明する。This method will be explained in more detail below.
硫酸の使用量は１−ヒドロキシ−２−ナフトエ酸エステ
ルに対し、１ないし８重量倍、特に本発明の目的を達す
るためには、■ないし５重量倍を使用し、硫酸濃度が８
０ないし９５％になるよう水で希釈する。添加する脂肪
族飽和炭化水素または芳香族炭化水素の具体例としては
ｎ−ヘキサン、ｎ−ヘプタン、オクタン、シクロヘキサ
ン、デカリン、トルエン、キシレンなどがあげられ、硫
酸の使用量に対し、３ないし５０重量％添加する。The amount of sulfuric acid used is 1 to 8 times the weight of the 1-hydroxy-2-naphthoic acid ester, and in particular, to achieve the purpose of the present invention, the amount of sulfuric acid used is 1 to 5 times the weight of the 1-hydroxy-2-naphthoic acid ester, and the sulfuric acid concentration is 8 times.
Dilute with water to 0-95%. Specific examples of aliphatic saturated hydrocarbons or aromatic hydrocarbons to be added include n-hexane, n-heptane, octane, cyclohexane, decalin, toluene, xylene, etc., and the amount is 3 to 50% by weight based on the amount of sulfuric acid used. %Added.
第３級ブチル化剤は理論量の１．１ないし２０倍程度使
用する。反応は０〜１０℃で行なうのがよく、高すぎる
と副反応の割合が増加する。The tertiary butylating agent is used in an amount of about 1.1 to 20 times the theoretical amount. The reaction is preferably carried out at a temperature of 0 to 10°C; if the temperature is too high, the rate of side reactions will increase.
得られる７−第３級ブチル−１−ヒドロキシ−２−ナフ
トエ酸エステルは、通常の加水分解反応に付すことによ
って、目的とするナフトエ酸とすることができる。たと
えば、水酸化ナトリウムまたは水酸化カリウムなどでア
ルカリ性とし、室温から１００℃で数時間反応後、塩酸
または硫酸などで酸性にもどすことによって加水分解す
ることができる。The obtained 7-tertiary butyl-1-hydroxy-2-naphthoic acid ester can be converted into the desired naphthoic acid by subjecting it to a conventional hydrolysis reaction. For example, it can be hydrolyzed by making it alkaline with sodium hydroxide or potassium hydroxide, reacting for several hours at room temperature to 100°C, and then returning it to acidity with hydrochloric acid or sulfuric acid.
原料としてのナフトエ酸エステルは、ナフトエ酸を通常
のニス萎ル化反応に付すことによって得られるが、たと
えば、脱水触媒（ｐ−トルエンスルホン酸など）または
三塩化リンなどの存在下に、反応に不活性な溶媒（ベン
ゼン、キシレン、クロロホルム、塩化メチレンなど）中
、室温から用いる溶媒の沸点までの温度で１〜１５時間
反応させるか、さらに、ジメチルホルムアミドなどの溶
媒中、水酸化ナトリウムなどで金属塩として、これにア
ルコールから誘導されるハロゲン化物を反応させること
によっても製造することができる。このようにして得ら
れるナフトエ酸エステルのエステル部としては、アルキ
ル（メチル、エチル、プロピル、イソプロピル、ブチル
、イソブチル、第３級ブチル、ペンチル、イソペンチル
、ヘキシル、ヘプチル、オクチル、２−エチルヘキシル
、第３級オクチル、ノニル、デシルなど）、シクロアル
キル（シクロプロピル、シクロブチル、シクロペンチル
、シクロヘキシル、シクロヘプチルなど）、アリール（
フェニル、ナフチルなど）およびアラルキル（ベンジル
、フェニルエチル、フェニルプロピル、フェニルブチル
など）などとのエステルが用いられる。Naphthoic acid ester as a raw material can be obtained by subjecting naphthoic acid to a normal varnish hydrolysis reaction. Either react for 1 to 15 hours in an inert solvent (benzene, xylene, chloroform, methylene chloride, etc.) at a temperature from room temperature to the boiling point of the solvent used, or further react with sodium hydroxide, etc. in a solvent such as dimethylformamide. It can also be produced as a salt by reacting it with a halide derived from an alcohol. The ester part of the naphthoic acid ester obtained in this way includes alkyl (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, tertiary butyl, octyl, nonyl, decyl, etc.), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.), aryl (
(phenyl, naphthyl, etc.) and aralkyls (benzyl, phenylethyl, phenylpropyl, phenylbutyl, etc.).
一般弐Ｎ）の化合物は、１−ヒドロキシ−２−ナフトエ
酸の親油性が高められた化合物であり、アスペルギルス
菌、タラトスポリウム菌、ケトミウム菌などのカビ類に
対し抗カビ作用を有し、抗カビ剤として有用であるばか
りでな（、工業用化学品の合成中間体としても使用でき
る。Compound 2N) is a compound with increased lipophilicity of 1-hydroxy-2-naphthoic acid, and has antifungal activity against molds such as Aspergillus, Talatosporium, and Chaetomium. Not only is it useful as a chemical agent, but it can also be used as a synthetic intermediate for industrial chemicals.
本発明の化合物を抗カビ剤として使用する場合、懸濁液
剤、溶液剤、乳剤、ペースト剤、粉剤などに調剤するこ
とができ、０．０５〜５０重量％、好ましくは０．１〜
１０重量％配合するとよい、また、公知の抗カビ剤と併
用することも可能である。When the compound of the present invention is used as an antifungal agent, it can be formulated into a suspension, solution, emulsion, paste, powder, etc., and is 0.05 to 50% by weight, preferably 0.1 to 50% by weight.
It is preferable to mix 10% by weight, and it is also possible to use it in combination with a known antifungal agent.
以下、実施例により本発明を具体的に説明するが、本発
明はそれらにより限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例１
濃硫酸５２０ｇに水９２ｇを加えた後、１−ヒドロキシ
−２−ナフトエ酸メチルエステル５５ｇを加え良く撹拌
し、トルエン２０ｇを注加する。Example 1 After adding 92 g of water to 520 g of concentrated sulfuric acid, 55 g of 1-hydroxy-2-naphthoic acid methyl ester was added, stirred well, and 20 g of toluene was added.
内容物を５〜１０℃に保ちながら攪拌下に第３級ブタノ
ール８０ｇを２時間で滴下する。滴下終了後、同温度で
１時間攪拌反応する。反応液をトルエン１５０ｍ１で抽
出し、硫酸層を分液分離する。80 g of tertiary butanol is added dropwise over 2 hours while stirring while keeping the contents at 5 to 10°C. After completion of the dropwise addition, the mixture was stirred and reacted at the same temperature for 1 hour. The reaction solution was extracted with 150 ml of toluene, and the sulfuric acid layer was separated.
トルエン層に水酸化ナトリウム７．５ｇを水２２０ｍ１
にとかした溶液を加え、５０〜５５℃で２時間攪拌する
。水層を分別し、さらにトルエン層に水酸化ナトリウム
１５ｇを水２２０ｍ１にとかした溶液を加え、８０〜８
５℃で４時間攪拌する。水層を分別し、硫酸酸性とした
後、酢酸エチル２００ｍ１で抽出し、抽出液を水洗し、
乾燥後濃縮する。Add 7.5 g of sodium hydroxide to the toluene layer and 220 ml of water.
Add the dissolved solution and stir at 50-55°C for 2 hours. The aqueous layer was separated, and a solution of 15 g of sodium hydroxide dissolved in 220 ml of water was added to the toluene layer.
Stir at 5°C for 4 hours. The aqueous layer was separated, acidified with sulfuric acid, extracted with 200ml of ethyl acetate, and the extract was washed with water.
Concentrate after drying.
得られた結晶を四塩化炭素とｎ−ヘキサンとの３：１混
合溶媒から再結晶すると、融点２００〜２０１’Ｃの７
−第３級ブチル−１−ヒドロキシ−２−ナフトエ酸４２
ｇが得られた（ＨＰＬＣ分析による含量：９８．５面積
％、質量スペクトル：分子イオンピーク＝２４４）。When the obtained crystals are recrystallized from a 3:1 mixed solvent of carbon tetrachloride and n-hexane, a 7.
-Tertiary butyl-1-hydroxy-2-naphthoic acid 42
(Content by HPLC analysis: 98.5 area %, mass spectrum: molecular ion peak = 244).
実施例２
トルエンの代りにキシレンを用いて実施例１と同様に反
応、処理すると、融点１９６〜１９９℃の白色結晶４０
ｇが得られた。７−第３級ブチル−１−ヒドロキシ−２
−ナフトエ酸のＨＰＬＣ分析による含量は９５．２％で
あった。Example 2 When the reaction and treatment were carried out in the same manner as in Example 1 using xylene instead of toluene, white crystals with a melting point of 196 to 199°C were obtained.
g was obtained. 7-tert-butyl-1-hydroxy-2
-The content of naphthoic acid by HPLC analysis was 95.2%.
実施例３
トルエンの代りにｎ−ヘキサンまたはシクロヘキサンを
用いた場合、および溶媒を用いない場合について実施例
１と同様に反応、処理した結果、７−第３級ブチル−１
−ヒドロキシ−２−ナフトエ酸の収量、含量、収率は次
の第１表に示す通りであった。Example 3 As a result of reaction and treatment in the same manner as in Example 1 when n-hexane or cyclohexane was used instead of toluene and when no solvent was used, 7-tertiary butyl-1
The yield, content, and yield of -hydroxy-2-naphthoic acid were as shown in Table 1 below.
第 １ 表Chapter 1 Table
Claims (1)
ナフトエ酸。[Claims] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 7-tert-butyl-1-hydroxy-2-
Naphthoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29457386A JPS63145254A (en) | 1986-12-09 | 1986-12-09 | Naphthoic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29457386A JPS63145254A (en) | 1986-12-09 | 1986-12-09 | Naphthoic acid derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63145254A true JPS63145254A (en) | 1988-06-17 |
Family
ID=17809528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29457386A Pending JPS63145254A (en) | 1986-12-09 | 1986-12-09 | Naphthoic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63145254A (en) |
-
1986
- 1986-12-09 JP JP29457386A patent/JPS63145254A/en active Pending
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