JP2015054859A - Gallic acid-formaldehyde addition condensation product - Google Patents
Gallic acid-formaldehyde addition condensation product Download PDFInfo
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- JP2015054859A JP2015054859A JP2013186849A JP2013186849A JP2015054859A JP 2015054859 A JP2015054859 A JP 2015054859A JP 2013186849 A JP2013186849 A JP 2013186849A JP 2013186849 A JP2013186849 A JP 2013186849A JP 2015054859 A JP2015054859 A JP 2015054859A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000007859 condensation product Substances 0.000 title claims abstract description 17
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 22
- 229940074391 gallic acid Drugs 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000005011 phenolic resin Substances 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 150000007522 mineralic acids Chemical class 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 abstract description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 abstract description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004327 boric acid Substances 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 abstract description 2
- 229940098779 methanesulfonic acid Drugs 0.000 abstract description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 235000006408 oxalic acid Nutrition 0.000 abstract description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001002 functional polymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- IUTKPPDDLYYMBE-UHFFFAOYSA-N 3,4,5-trihydroxybenzoic acid;hydrate Chemical compound O.OC(=O)C1=CC(O)=C(O)C(O)=C1 IUTKPPDDLYYMBE-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XUZLXCQFXTZASF-UHFFFAOYSA-N nitro(phenyl)methanol Chemical compound [O-][N+](=O)C(O)C1=CC=CC=C1 XUZLXCQFXTZASF-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 alicyclic hydrocarbons Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Description
本発明は、没食子酸−ホルムアルデヒド付加縮合生成物及びその製造方法に関する。この没食子酸−ホルムアルデヒド付加縮合生成物は成形材料や機能性ポリマー等の原料として利用できる。 The present invention relates to a gallic acid-formaldehyde addition condensation product and a method for producing the same. This gallic acid-formaldehyde addition condensation product can be used as a raw material for molding materials and functional polymers.
フェノール樹脂として、特定量のメタクレゾールとパラクレゾールとサリチル酸等の他のフェノール類と、ホルムアルデヒド及び／又はパラアルデヒドとを酸性触媒のもとで反応させて得られるノボラック型フェノール樹脂が知られている（特許文献１）。このノボラック型フェノール樹脂はフォトレジスト用樹脂として用いられる。 As a phenolic resin, a novolak type phenolic resin obtained by reacting a specific amount of other phenols such as metacresol, paracresol and salicylic acid with formaldehyde and / or paraaldehyde under an acidic catalyst is known. (Patent Document 1). This novolac type phenol resin is used as a resin for photoresist.
本発明の目的は、分子内に多数の反応性官能基を有する新規なフェノール樹脂とその製造方法を提供することにある。 The objective of this invention is providing the novel phenol resin which has many reactive functional groups in a molecule | numerator, and its manufacturing method.
本発明者らは、上記目的を達成するため鋭意検討した結果、没食子酸とホルムアルデヒド又はパラホルムアルデヒドとを酸の存在下で反応させると、分子内に多数の反応性官能基を有する新規なフェノール樹脂が得られることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have made a novel phenol resin having a large number of reactive functional groups in the molecule when gallic acid is reacted with formaldehyde or paraformaldehyde in the presence of an acid. Was found and the present invention was completed.
すなわち、本発明は、没食子酸とホルムアルデヒド又はパラホルムアルデヒドとを酸の存在下で反応させて得られる没食子酸−ホルムアルデヒド付加縮合生成物を提供する。 That is, the present invention provides a gallic acid-formaldehyde addition condensation product obtained by reacting gallic acid with formaldehyde or paraformaldehyde in the presence of an acid.
前記没食子酸−ホルムアルデヒド付加縮合生成物には、下記式（２）、（３）、（４）、（５）、（６）又は（７）で表される構造を有する化合物が含まれる。
本発明は、また、没食子酸とホルムアルデヒド又はパラホルムアルデヒドとを、酸の存在下で反応させることを特徴とする没食子酸−ホルムアルデヒド付加縮合生成物の製造方法を提供する。 The present invention also provides a method for producing a gallic acid-formaldehyde addition condensation product, characterized by reacting gallic acid with formaldehyde or paraformaldehyde in the presence of an acid.
本発明によれば、新規なフェノール樹脂が提供される。このフェノール樹脂は、一般的なフェノール樹脂と同様、硬化剤の存在下または不存在下で熱により硬化するので、熱硬化性樹脂として利用できる。また、分子内に多数の水酸基及びカルボキシル基を有するため、修飾により目的、用途に応じた種々の機能を付与することができる。このため、本発明の没食子酸−ホルムアルデヒド付加縮合生成物は成形材料や機能性ポリマー等の原料として利用できる。 According to the present invention, a novel phenol resin is provided. Since this phenol resin is cured by heat in the presence or absence of a curing agent, like a general phenol resin, it can be used as a thermosetting resin. Moreover, since it has many hydroxyl groups and carboxyl groups in a molecule | numerator, various functions according to the objective and a use can be provided by modification. For this reason, the gallic acid-formaldehyde addition condensation product of this invention can be utilized as raw materials, such as a molding material and a functional polymer.
本発明の没食子酸−ホルムアルデヒド付加縮合生成物は、下記式（１）で表される没食子酸とホルムアルデヒド又はパラホルムアルデヒドとを酸の存在下で反応させて得られる化合物である。この没食子酸−ホルムアルデヒド付加縮合生成物には、前記式（２）、（３）、（４）、（５）、（６）、（７）で表される構造を有する化合物が含まれる。 The gallic acid-formaldehyde addition condensation product of the present invention is a compound obtained by reacting gallic acid represented by the following formula (1) with formaldehyde or paraformaldehyde in the presence of an acid. The gallic acid-formaldehyde addition condensation product includes a compound having a structure represented by the formulas (2), (3), (4), (5), (6), and (7).
本発明の没食子酸−ホルムアルデヒド付加縮合生成物は、没食子酸とホルムアルデヒド又はその等価体とを酸の存在下で反応させることにより製造できる。 The gallic acid-formaldehyde addition condensation product of the present invention can be produced by reacting gallic acid with formaldehyde or an equivalent thereof in the presence of an acid.
没食子酸として没食子酸水和物を用いてもよい。前記ホルムアルデヒドの等価体としては、反応条件下でホルムアルデヒドとして反応する化合物であればよく、例えば、パラホルムアルデヒドなどが挙げられる。 Gallic acid hydrate may be used as gallic acid. The formaldehyde equivalent may be a compound that reacts as formaldehyde under reaction conditions, and examples thereof include paraformaldehyde.
没食子酸とホルムアルデヒド又はその等価体との反応において、ホルムアルデヒド又はその等価体の使用量（ホルムアルデヒド換算）は、没食子酸１モルに対して、例えば、０．４〜１．０、好ましくは０．６〜０．９５である。 In the reaction of gallic acid with formaldehyde or its equivalent, the amount of formaldehyde or its equivalent used (in terms of formaldehyde) is, for example, 0.4 to 1.0, preferably 0.6 with respect to 1 mol of gallic acid. ~ 0.95.
前記酸としては、例えば、塩酸、硫酸、硝酸、リン酸、ホウ酸などの無機酸；シュウ酸、酢酸等のカルボン酸や、メタンスルホン酸、エタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、ナフタレンスルホン酸等のスルホン酸などの有機酸が挙げられる。これらの中でも、塩酸等の無機酸が好ましい。 Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; carboxylic acids such as oxalic acid and acetic acid, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, Examples thereof include organic acids such as p-toluenesulfonic acid and sulfonic acids such as naphthalenesulfonic acid. Among these, inorganic acids such as hydrochloric acid are preferable.
前記酸の使用量は、反応速度、副反応抑制の点を考慮して適宜選択できるが、通常、原料として用いる没食子酸に対して、例えば、０．００１〜１０重量％、好ましくは０．１〜５重量％である。 The amount of the acid used can be appropriately selected in consideration of the reaction rate and side reaction suppression, but is usually 0.001 to 10% by weight, preferably 0.1%, based on gallic acid used as a raw material. ~ 5% by weight.
反応は溶媒の存在下又は非存在下で行われる。溶媒としては、反応に不活性な溶媒であればよく、例えば、水；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ペンタン、ヘキサン、ヘプタン、オクタン、デカン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン等の脂環式炭化水素；これらの混合溶媒などが挙げられる。 The reaction is carried out in the presence or absence of a solvent. The solvent may be any solvent inert to the reaction, for example, water; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; cyclopentane, And alicyclic hydrocarbons such as cyclohexane; and mixed solvents thereof.
反応温度は、例えば、５０〜２００℃、好ましくは８０〜１５０℃である。反応時間は、例えば、０．１〜５０時間、好ましくは０．２〜１０時間である。 The reaction temperature is, for example, 50 to 200 ° C, preferably 80 to 150 ° C. The reaction time is, for example, 0.1 to 50 hours, preferably 0.2 to 10 hours.
反応の方法は特に限定されず、例えば、反応器に没食子酸とホルムアルデヒド又はその等価体と酸とを一括で仕込み、所定温度で反応させてもよく、また、反応器に没食子酸と酸とを仕込み、所定温度とした後、ホルムアルデヒド又はその等価体を反応器内に逐次添加してもよい。 The reaction method is not particularly limited. For example, gallic acid and formaldehyde or an equivalent thereof and an acid may be charged into a reactor at a time and reacted at a predetermined temperature. In addition, gallic acid and an acid may be added to the reactor. After charging and setting to a predetermined temperature, formaldehyde or an equivalent thereof may be sequentially added into the reactor.
反応後、沈殿、再沈殿等の慣用の分離精製手段を用いることにより没食子酸−ホルムアルデヒド付加縮合生成物を単離することができる。 After the reaction, the gallic acid-formaldehyde addition condensation product can be isolated by using conventional separation and purification means such as precipitation and reprecipitation.
こうして得られる没食子酸−ホルムアルデヒド付加縮合生成物は、テトラヒドロフラン、メタノール、アセトン、ジメチルスルホキシド等の溶媒に可溶であり、クロロホルム、水には不溶である。前記没食子酸−ホルムアルデヒド付加縮合生成物は、硬化剤の存在下または不存在下で熱により硬化するので、熱硬化性樹脂として利用できる。また、分子内に多数の水酸基及びカルボキシル基を有するため、修飾により目的、用途に応じた種々の機能を付与することができる。このため、成形材料や機能性ポリマー等の原料として利用できる。 The gallic acid-formaldehyde addition condensation product thus obtained is soluble in solvents such as tetrahydrofuran, methanol, acetone, dimethyl sulfoxide, and insoluble in chloroform and water. Since the gallic acid-formaldehyde addition condensation product is cured by heat in the presence or absence of a curing agent, it can be used as a thermosetting resin. Moreover, since it has many hydroxyl groups and carboxyl groups in a molecule | numerator, various functions according to the objective and a use can be provided by modification. For this reason, it can utilize as raw materials, such as a molding material and a functional polymer.
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
実施例１
窒素雰囲気下、冷却管を取り付けたガラス製のフラスコに没食子酸水和物（東京化成工業株式会社）１８ｇ、３７重量％ホルムアルデヒド水溶液（東京化成工業株式会社）７．４ｍＬ、濃塩酸水溶液（関東化学株式会社）０．１ｍＬ、純水１００ｍＬを仕込んだ。１１０℃のオイルバスで加熱還流し、１時間撹拌を続けた。次に、１００ｇの純水を加えた。デカンテーションにより上澄みを除去し、不溶部を、８０℃、真空下で６時間乾燥し、３．７ｇの赤褐色の生成物を得た。
Example 1
Under a nitrogen atmosphere, 18 g of gallic acid hydrate (Tokyo Kasei Kogyo Co., Ltd.), 7.4 mL of a 37 wt% formaldehyde aqueous solution (Tokyo Kasei Kogyo Co., Ltd.), concentrated hydrochloric acid aqueous solution (Kanto Chemical) Co., Ltd.) 0.1 mL and 100 mL of pure water were charged. The mixture was heated to reflux in an oil bath at 110 ° C. and stirred for 1 hour. Next, 100 g of pure water was added. The supernatant was removed by decantation, and the insoluble part was dried at 80 ° C. under vacuum for 6 hours to obtain 3.7 g of a reddish brown product.
前記生成物の溶解性を調べるため、ガラスサンプル瓶中に試料０．２ｍｇを溶媒１ｍＬに分散させ、溶解性を確認した。その結果、テトラヒドロフラン、メタノール、アセトン、ジメチルスルホキシドには溶解したが、クロロホルム、水には溶解しなかった。 In order to examine the solubility of the product, 0.2 mg of a sample was dispersed in 1 mL of a solvent in a glass sample bottle, and the solubility was confirmed. As a result, it was dissolved in tetrahydrofuran, methanol, acetone and dimethyl sulfoxide, but was not dissolved in chloroform and water.
没食子酸及び前記生成物の1Ｈ−ＮＭＲスペクトル、13Ｃ−ＮＭＲスペクトルを測定した（溶媒：ＤＭＳＯ−ｄ6）。没食子酸及び前記生成物の1Ｈ−ＮＭＲスペクトルを図１に示す（上が没食子酸、下が生成物）。没食子酸及び前記生成物の13Ｃ−ＮＭＲスペクトルを図２に示す。
また、前記生成物について下記の条件で質量分析（ＦＡＢ−ＭＡＳＳ）を行った。結果を図３に示す（上がｐｏｓｉｔｉｖｅ、下がｎｅｇａｔｉｖｅ）。
装置：日本電子製「ＳＸ−１０２Ａ」
測定モード：ＦＡＢ（ｐｏｓｉｔｉｖｅ，ｎｅｇａｔｉｖｅ）
マトリックス：ＮＢＡ（ニトロベンジルアルコール）
加速電圧：８ｋＶ
測定範囲：１０〜２０００ｍ／ｚ
1 H-NMR spectrum and 13 C-NMR spectrum of gallic acid and the product were measured (solvent: DMSO-d 6 ). The 1 H-NMR spectrum of gallic acid and the product is shown in FIG. 1 (upper is gallic acid, lower is the product). The 13 C-NMR spectrum of gallic acid and the product is shown in FIG.
The product was subjected to mass spectrometry (FAB-MASS) under the following conditions. The results are shown in FIG. 3 (the upper is positive and the lower is negative).
Device: JEOL “SX-102A”
Measurement mode: FAB (positive, negative)
Matrix: NBA (nitrobenzyl alcohol)
Acceleration voltage: 8 kV
Measurement range: 10 to 2000 m / z
1Ｈ−ＮＭＲスペクトル、13Ｃ−ＮＭＲスペクトル及びマススペクトルを解析した結果、下記式（２）（Ｅｘａｃｔ Ｍａｓｓ＝３５２）、（３）（Ｅｘａｃｔ Ｍａｓｓ＝３６４）、（４）（Ｅｘａｃｔ Ｍａｓｓ＝３６４）、（５）（Ｅｘａｃｔ Ｍａｓｓ＝３６４）、（６）（Ｅｘａｃｔ Ｍａｓｓ＝３６４）、及び（７）（Ｅｘａｃｔ Ｍａｓｓ＝５３４）で表される化合物の生成を確認した。
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| JP2013186849A JP2015054859A (en) | 2013-09-10 | 2013-09-10 | Gallic acid-formaldehyde addition condensation product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013186849A JP2015054859A (en) | 2013-09-10 | 2013-09-10 | Gallic acid-formaldehyde addition condensation product |
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| JP2015054859A true JP2015054859A (en) | 2015-03-23 |
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| JP2013186849A Pending JP2015054859A (en) | 2013-09-10 | 2013-09-10 | Gallic acid-formaldehyde addition condensation product |
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| JP (1) | JP2015054859A (en) |
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2013
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