JPH01238548A - 1,4,5,8-tetrakis(hydroxymethyl)naphthalene, its derivative and production thereof - Google Patents
1,4,5,8-tetrakis(hydroxymethyl)naphthalene, its derivative and production thereofInfo
- Publication number
- JPH01238548A JPH01238548A JP6687688A JP6687688A JPH01238548A JP H01238548 A JPH01238548 A JP H01238548A JP 6687688 A JP6687688 A JP 6687688A JP 6687688 A JP6687688 A JP 6687688A JP H01238548 A JPH01238548 A JP H01238548A
- Authority
- JP
- Japan
- Prior art keywords
- naphthalene
- tetrakis
- hydroxymethyl
- formula
- tetracarboxylic acid
- 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.)
- Granted
Links
- NMFXRKRVTPFPKQ-UHFFFAOYSA-N [4,5,8-tris(hydroxymethyl)naphthalen-1-yl]methanol Chemical compound C1=CC(CO)=C2C(CO)=CC=C(CO)C2=C1CO NMFXRKRVTPFPKQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 21
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 150000008050 dialkyl sulfates Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical group 0.000 claims abstract 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 15
- -1 alkali metal salt Chemical class 0.000 abstract description 4
- 238000006266 etherification reaction Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- QGAXWPQVFUUSGN-UHFFFAOYSA-N tetramethyl naphthalene-1,4,5,8-tetracarboxylate Chemical compound C1=CC(C(=O)OC)=C2C(C(=O)OC)=CC=C(C(=O)OC)C2=C1C(=O)OC QGAXWPQVFUUSGN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 229920002614 Polyether block amide Polymers 0.000 abstract 1
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 239000012374 esterification agent Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PBLNHHSDYFYZNC-UHFFFAOYSA-N (1-naphthyl)methanol Chemical compound C1=CC=C2C(CO)=CC=CC2=C1 PBLNHHSDYFYZNC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- IMXKNSVCKZMEOY-UHFFFAOYSA-N [2,3,4-tris(hydroxymethyl)naphthalen-1-yl]methanol Chemical class OCC1=C(C(=C(C2=CC=CC=C12)CO)CO)CO IMXKNSVCKZMEOY-UHFFFAOYSA-N 0.000 description 1
- USNWHLWKVPCAFF-UHFFFAOYSA-N [4,5,8-tris(acetyloxymethyl)naphthalen-1-yl]methyl acetate Chemical compound CC(=O)OCc1ccc(COC(C)=O)c2c(COC(C)=O)ccc(COC(C)=O)c12 USNWHLWKVPCAFF-UHFFFAOYSA-N 0.000 description 1
- DINZUYYYXDLSJE-UHFFFAOYSA-N [8-(hydroxymethyl)naphthalen-1-yl]methanol Chemical compound C1=CC(CO)=C2C(CO)=CC=CC2=C1 DINZUYYYXDLSJE-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000005457 ice water Substances 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、１．４．５．８−テトラキス（ヒドロキシメ
チル）ナフタレン、その誘導体、およびこれらの製造方
法に関し、より詳細には、１，４．５゜８−テトラキス
（ヒドロキシメチル）ナフタレンおよびその誘導体の製
造原料であるナフタレン−１，４，５，８−テトラカル
ボン酸テトラアルキルエステルの製造方法、新規化合物
であるｌ、４゜５．８−テトラキス（ヒドロキシメチル
）ナフタレンおよびその誘導体、ならびにこれら化合物
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to 1.4.5.8-tetrakis(hydroxymethyl)naphthalene, derivatives thereof, and methods for producing these, and more particularly, 4.5゜Production method of naphthalene-1,4,5,8-tetracarboxylic acid tetraalkyl ester, which is a raw material for the production of 8-tetrakis(hydroxymethyl)naphthalene and its derivatives, 1, a new compound, 4゜5. The present invention relates to 8-tetrakis(hydroxymethyl)naphthalene and its derivatives, and methods for producing these compounds.
ナフタレン−１，４，５，８−テトラカルボン酸テトラ
アルキルエステルの製造方法としては、ナフタレン−１
，４，５，８−テトラカルボン酸テトラメチルエステル
がナフタレン−１，４，５，８−テトラカルボン酸の銀
塩とヨウ化メチルとから得られることが文献に記載され
ている［ Ｊ 、 Ｗ 、 Ｃｏ ｏ ｋ ＋Ｒ，５ｃ
ｈｏｅｎｔａｌ、Ｊ、Ｃｈｅｍ、Ｓｏｃ、４７（１９５
０） ）。As a method for producing naphthalene-1,4,5,8-tetracarboxylic acid tetraalkyl ester, naphthalene-1
, 4,5,8-tetracarboxylic acid tetramethyl ester is obtained from the silver salt of naphthalene-1,4,5,8-tetracarboxylic acid and methyl iodide [J, W , Cook +R,5c
Hoental, J. Chem, Soc., 47 (195
0) ).
しかしながら、この文献には反応条件や反応収率など、
詳細な具体的製造条件については、全く記載されていな
い。この文献記載の方法は、仮に反応収率が良いとして
も、高価な銀塩やヨウ化メチルを使用するので経済上問
題があり、また化学反応面からしても大規模生産化は技
術的に困難である。However, this literature does not include the reaction conditions, reaction yield, etc.
Detailed specific manufacturing conditions are not described at all. Even if the method described in this literature has a good reaction yield, it is economically problematic because it uses expensive silver salts and methyl iodide, and it is also technically difficult to achieve large-scale production from the chemical reaction standpoint. Have difficulty.
一方、ナフタレンのペリ位（１，８位）にヒドロキシメ
チル基（Ｃ）ＩｚＯＨ）が置換した１、８−ビス（ヒド
ロキシメチル）ナフタレンは良く知られた化合物である
。On the other hand, 1,8-bis(hydroxymethyl)naphthalene in which a hydroxymethyl group (C)IzOH) is substituted at the peri-position (1,8-position) of naphthalene is a well-known compound.
しかしながら、ナフタレン環の、更に他のペリ位（４，
５位）にもヒドロキシメチル基が置換したビスペリ置換
体の１．４．５．８−テトラキス（ヒドロキシメチル）
ナフタレンは、応用面での幅広い用途が期待されている
にもかかわらず、合成化学上の困難さから、現在に至る
まで未知化合物である。However, other peri-positions (4,
1.4.5.8-tetrakis(hydroxymethyl), a bisperi-substituted product in which a hydroxymethyl group is also substituted (5-position)
Although naphthalene is expected to have a wide range of applications, it remains an unknown compound until now due to difficulties in synthetic chemistry.
上記のように、ナフタレン−１，４，５，８−テトラカ
ルボン酸テトラアルキルエステルの従来の製造方法は、
高価な原料を使用し、大量生産が困難であった。As mentioned above, the conventional method for producing naphthalene-1,4,5,8-tetracarboxylic acid tetraalkyl ester is as follows:
It used expensive raw materials and was difficult to mass produce.
すなわち本発明は、安価な原料を用いて高収率で、しか
も大量生産可能な、ナフタレン＝１゜４．５．８−テト
ラカルボン酸テトラアルキルエステルの製造方法を提供
するものである。また、１．４．５．８−テトラキス
（ヒドロキシメチル）ナフタレンおよびその誘導体は現
在に至るまで知られていなかった。That is, the present invention provides a method for producing tetraalkyl naphthalene=1°4.5.8-tetracarboxylic acid ester, which can be produced in high yield and in large quantities using inexpensive raw materials. Also, 1.4.5.8-tetrakis
(Hydroxymethyl)naphthalene and its derivatives were unknown until now.
すなわち、本発明は新規化合物の１．４，５．８−テト
ラキス（ヒドロキシメチル）ナフタレンおよびその誘導
体と、ナフタレン−１，４，５，８−テトラカルボン酸
テトラアルキルエステルを原料とするこれら化合物の製
造方法を提供するものである。That is, the present invention relates to novel compounds such as 1,4,5,8-tetrakis(hydroxymethyl)naphthalene and its derivatives, and the preparation of these compounds using naphthalene-1,4,5,8-tetracarboxylic acid tetraalkyl esters as raw materials. A manufacturing method is provided.
上記問題点を解決し、目的を達成するための本発明の、
下記一般式（１）で示されるナフタレン−１，４，５，
８−テトラカルボン酸テトラアルキルエステルの製造方
法は、ナフタレン−１，４゜５．８−テトラカルボン酸
のテトラアルカリ金属塩に硫酸ジアルキルを作用させる
ことを特徴とするものである。The present invention solves the above problems and achieves the objectives.
Naphthalene-1,4,5, represented by the following general formula (1),
The method for producing 8-tetracarboxylic acid tetraalkyl ester is characterized by reacting a tetraalkyl metal salt of naphthalene-1,4°5.8-tetracarboxylic acid with a dialkyl sulfate.
ただしく１）式中、ＲＩはＣ３〜Ｃ２アルキル基である
。However, in the formula 1), RI is a C3-C2 alkyl group.
また、本発明に係る新規化合物の１．４，５．８−テト
ラキス（ヒドロキシメチル）ナフタレンは、下記構造式
（１）で示される。Further, 1,4,5,8-tetrakis(hydroxymethyl)naphthalene, which is a new compound according to the present invention, is represented by the following structural formula (1).
）ＩＱ）ｌｔｃ ＧＨｚＯＨ
更に本発明に係る新規化合物の１．４．５．８−テトラ
キス（ヒドロキシメチル）ナフタレン誘導体は下記一般
式（ｎ）で表わされる。) IQ) ltc GHzOH Furthermore, the 1.4.5.8-tetrakis(hydroxymethyl)naphthalene derivative of the novel compound according to the present invention is represented by the following general formula (n).
ただしくｎ）式中、ＯＲ”はアルコール残基またはカル
ボン酸残基である。(n) In the formula, OR'' is an alcohol residue or a carboxylic acid residue.
そして上記構造式（１）で示される１、４．５．８−テ
トラキス（ヒドロキシメチル）ナフタレンは、上記一般
式（１）で示される１、４．５．８−テトラカルボン酸
テトラアルキルエステルを水素化ジアルキルアルミニウ
ムで還元することにより製造される。1,4,5.8-tetrakis(hydroxymethyl)naphthalene represented by the above structural formula (1) is a 1,4,5.8-tetracarboxylic acid tetraalkyl ester represented by the above general formula (1). Produced by reduction with dialkyl aluminum hydride.
また、上記一般式（■゛）モ示される１、４，５．８−
テトラキス（ヒドロキシメチル）ナフタレン誘導体は、
上記構造式（１）で示される１、４，５゜８−テトラキ
ス（ヒドロキシメチル）ナフタレンをエーテル化剤また
はエステル化剤で処理することにより製造される。In addition, 1, 4, 5.8- shown in the above general formula (■゛)
Tetrakis(hydroxymethyl)naphthalene derivatives are
It is produced by treating 1,4,5°8-tetrakis(hydroxymethyl)naphthalene represented by the above structural formula (1) with an etherifying agent or an esterifying agent.
以下、本発明について説明する。The present invention will be explained below.
本発明のナフタレン−１，４，５，８−テトラカルボン
酸テトラアルキルエステルの製造方法によれば、反応は
水溶液中で行なわれる。すなわち、炭酸ナトリウムや炭
酸カリウムなどのアルカリ金属炭酸塩の水溶液に、ナフ
タレン−１，４，５，８−テトラカルボン酸を加えてナ
フタレン−１，４゜５．８−テトラカルボン酸テトラア
ルカリ金属塩の水溶液を製造する。According to the method for producing naphthalene-1,4,5,8-tetracarboxylic acid tetraalkyl ester of the present invention, the reaction is carried out in an aqueous solution. That is, naphthalene-1,4,5,8-tetracarboxylic acid is added to an aqueous solution of an alkali metal carbonate such as sodium carbonate or potassium carbonate to form a tetraalkali metal naphthalene-1,4°5.8-tetracarboxylic acid salt. Produce an aqueous solution of
この水溶液に硫酸ジアルキル（Ｒ’□Ｓ０４、ただしＲ
ＩはＣ，−ＣＲのアルキル基である）を滴下して、エス
テル化反応を行なう。硫酸ジアルキルを滴下した後に、
再びアルカリ金属炭酸塩、次いで硫酸ジアルキルを添加
し、この操作を数回繰り返してエステル化反応を完結さ
せる。すなわち、アルカリ金属炭酸塩を３倍量、硫酸ジ
アルキルを５倍量と過剰に使用し、これらを夫々、数回
に分けて添加する。Add dialkyl sulfate (R'□S04, however, R
(I is an alkyl group of C, -CR) is added dropwise to carry out an esterification reaction. After dropping the dialkyl sulfate,
The alkali metal carbonate and then the dialkyl sulfate are added again, and this operation is repeated several times to complete the esterification reaction. That is, three times the amount of alkali metal carbonate and five times the amount of dialkyl sulfate are used in excess, and these are added in several portions, respectively.
反応は下記反応式で示すように進行し、反応温度は室温
〜６０℃の範囲である。The reaction proceeds as shown in the following reaction formula, and the reaction temperature is in the range of room temperature to 60°C.
エステル化反応の進行と共に、生成物のテトラアルキル
エステルが白色沈澱物として反応液から分離してくるの
で、反応終了後に反応液を冷却して、この沈澱物を濾過
、捕集すれば、下記一般式（１）のナフタレン−１，４
，５，８−テトラカルボン酸テトラアルキルエステルを
得ることができる。As the esterification reaction progresses, the tetraalkyl ester of the product separates from the reaction solution as a white precipitate, so if the reaction solution is cooled after the reaction is completed and this precipitate is filtered and collected, the following general Naphthalene-1,4 of formula (1)
, 5,8-tetracarboxylic acid tetraalkyl ester can be obtained.
Ｍｅ：アルカリ金属
（Ｉ）
ただしく１）式中、Ｒ１は０１〜Ｃ２のアルキル基であ
る。Me: Alkali metal (I) In formula 1), R1 is an alkyl group of 01 to C2.
なお、ナフタレン−１，４，５，８−テトラカルボン酸
テトラアルキルエステル（１）製造の原料となるナフタ
レン−１，４，５，８−テトラカルボン酸（３）は、通
常、市販されているナフタレン−１，４，５，８−テト
ラカルボン酸二無水物（２）をアルカリ存在下に加水分
解することにより得られる。Note that naphthalene-1,4,5,8-tetracarboxylic acid (3), which is a raw material for producing naphthalene-1,4,5,8-tetracarboxylic acid tetraalkyl ester (1), is usually commercially available. It is obtained by hydrolyzing naphthalene-1,4,5,8-tetracarboxylic dianhydride (2) in the presence of an alkali.
次に本発明においては、上記（Ｉ）式のテトラアルキル
エステルを出発原料として、１．４．５゜８−テトラキ
ス（ヒドロキシメチル）ナフタレンおよびその誘導体を
製造する。Next, in the present invention, 1.4.5°8-tetrakis(hydroxymethyl)naphthalene and its derivatives are produced using the tetraalkyl ester of formula (I) as a starting material.
まず、ナフタレン−１，４，５，８−テトラカルボン酸
テトラアルキルエステル、たとえばテトラメチルエステ
ルを、不活性有機溶媒、たとえばベンゼンに溶解し、水
素化ジアルキルアルミニウム、たとえば水素化ジイソプ
チルアルミニウ ム（（ｉ−Ｂｕ）ｚＡＩＨ）で処理す
ると、エステル基（−ＣＯＯＲりがヒドロキシメチル（
−ＣＩ、ＯＨ）に還元されて下記構造式（１）の新規化
合物１．４．５゜８−テトラキス（ヒドロキシメチル）
ナフタレンが得られる。First, a naphthalene-1,4,5,8-tetracarboxylic acid tetraalkyl ester, such as tetramethyl ester, is dissolved in an inert organic solvent, such as benzene, and a dialkyl aluminum hydride, such as diisoptylaluminum hydride ( (i-Bu)zAIH), the ester group (-COOR) becomes hydroxymethyl (
-CI, OH) to produce a novel compound of the following structural formula (1): 1.4.5°8-tetrakis(hydroxymethyl)
Naphthalene is obtained.
次に得られた１、４．５．８−テトラキス（ヒドロキシ
メチル）ナフタレン（１）をエーテル化剤で処理すると
、１．４．５．８−テトラキス（ヒドロキシメチル）ナ
フタレンのテトラエーテル誘導体（ＩＩＩ）を得ること
ができる。Next, when the obtained 1,4.5.8-tetrakis(hydroxymethyl)naphthalene (1) is treated with an etherification agent, the tetraether derivative of 1.4.5.8-tetrakis(hydroxymethyl)naphthalene (III ) can be obtained.
ＨＯＨｚＣＣＨｚＯＨＲ”ＯＬＣＣＨｚＯＲ”（１）
（ＩＩＩ）（ＩＩＩ）
式中、ＯＲ”はアルコール残基を示す。HOHzCCHzOHR"OLCCHzOR" (1)
(III) (III)
In the formula, OR'' represents an alcohol residue.
エーテル化剤としては、ヨウ化メチル、臭化エチルなど
のハロゲン化アルキル等を用いることができる。As the etherification agent, alkyl halides such as methyl iodide and ethyl bromide can be used.
反応は、１．４，５．８−テトラキス（ヒドロキシメチ
ル）ナフタレン（１）をまず塩基、たとえば水素化ナト
リウムで処理して、１．４．５．８−テトラキス（ヒド
ロキシメチル）ナフタレンのテトラアルコキシド塩に変
えた後、次いでこれにハロゲン化アルキルを作用させて
、活性アルコキシドアニオンとアルキル基との間でエー
テル結合を形成させることにより、１，４．５．８−テ
トラキス（ヒドロキシメチル）ナフタレンのテトラエー
テル誘導体（ＩＩＩ）が得られる。The reaction involves first treating 1,4,5,8-tetrakis(hydroxymethyl)naphthalene (1) with a base, such as sodium hydride, to form the tetraalkoxide of 1,4,5,8-tetrakis(hydroxymethyl)naphthalene. After converting it into a salt, it is then treated with an alkyl halide to form an ether bond between the active alkoxide anion and the alkyl group, thereby converting 1,4.5.8-tetrakis(hydroxymethyl)naphthalene into a salt. A tetraether derivative (III) is obtained.
また、１，４．５．８−テトラキス（ヒドロキシメチル
）ナフタレン（１）にアシル化剤などのエステル化剤を
作用させてエステル化反応を行なうと、１．４，５．８
−テトラキス（ヒドロキシメチル）ナフタレンのテトラ
エステル誘導体（ＩＶ）である１、４．５．８−テトラ
キス（アシルオキシメチル）ナフタレンが得られる。Furthermore, when an esterifying agent such as an acylating agent is applied to 1,4.5.8-tetrakis(hydroxymethyl)naphthalene (1) to perform an esterification reaction, 1.4,5.8
1,4.5.8-tetrakis(acyloxymethyl)naphthalene, which is a tetraester derivative (IV) of -tetrakis(hydroxymethyl)naphthalene, is obtained.
（１） （ＩＶ）（ＩＶ）式中
、ＯＲ”はカルボン酸残基である。(1) (IV) (IV) In the formula, OR'' is a carboxylic acid residue.
アシル化剤としては、無水酢酸、無水安息香酸等のカル
ボン酸無水物や、塩化アセチル、塩化ベンゾイル等のハ
ロゲン化アシルなどが用いられる。As the acylating agent, carboxylic acid anhydrides such as acetic anhydride and benzoic anhydride, and acyl halides such as acetyl chloride and benzoyl chloride are used.
反応は、ピリジンなどの溶媒中で行なわれ、その反応温
度はアシル化剤の種類により変化するが、一般にはアシ
ル化剤添加直後が室温ないし８０℃、その後の放置温度
がＯ℃〜室温の範囲である。The reaction is carried out in a solvent such as pyridine, and the reaction temperature varies depending on the type of acylating agent, but generally it is room temperature to 80°C immediately after the addition of the acylating agent, and the temperature thereafter is in the range of 0°C to room temperature. It is.
得られた１、４．５．８−テトラキス（ヒドロキシメチ
ル）ナフタレンのテトラエーテル誘導体およびテトラエ
ステル誘導体は、いずれも新規化合物である。The obtained tetraether derivative and tetraester derivative of 1,4.5.8-tetrakis(hydroxymethyl)naphthalene are both new compounds.
以下、本発明を実施例により、さらに詳述する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
参考例：ナフタレン−１，４，５，８−テトラカルボン
酸の製造。Reference example: Production of naphthalene-1,4,5,8-tetracarboxylic acid.
約２Ｎの水酸化ナトリウム水溶液２．１！！にナフタレ
ン−１，４，５，８−テトラカルボン酸二無水物１７２
ｇを加えた。Approximately 2N sodium hydroxide aqueous solution 2.1! ! Naphthalene-1,4,5,8-tetracarboxylic dianhydride 172
g was added.
懸濁液を約８０℃に加熱しながら１晩攪拌した。The suspension was stirred overnight while heating to about 80°C.
室温に冷却後、反応混合物中の不溶物質を吸引濾過して
除き、濾液に水冷下、希硫酸を加えて酸性にした。析出
した固体を吸引濾過して集め、希塩酸、次いで水で洗い
乾燥すると、はとんど無色固体のナフタレン−１，４，
５，８−テトラカルボン酸が得られた（１８４ｇ、収率
９５％）。After cooling to room temperature, insoluble substances in the reaction mixture were removed by suction filtration, and dilute sulfuric acid was added to the filtrate under water cooling to make it acidic. The precipitated solids were collected by suction filtration, washed with dilute hydrochloric acid and then with water, and dried to yield mostly colorless solid naphthalene-1,4,
5,8-tetracarboxylic acid was obtained (184 g, yield 95%).
鋼、ｐ、＞３６０℃
元素分析：測定値Ｃ；５５．５０． Ｈ：２．６０計算
値Ｃ；５５．２７． Ｈ：２．６５（ＣＩ４Ｈ１０１）
実施例１
炭酸ナトリウム１６ｇを水２００ｄに溶かした溶液にナ
フタレン−１，４，５，８−テトラカルボン酸１５．２
ｇを少しずつ添加した。カルボン酸が反応するにつれ炭
酸ガスの気泡が激しく発生した。Steel, p, >360°C Elemental analysis: Measured value C; 55.50. H: 2.60 Calculated value C; 55.27. H:2.65 (CI4H101)
Example 1 To a solution of 16 g of sodium carbonate dissolved in 200 d of water was added 15.2 g of naphthalene-1,4,5,8-tetracarboxylic acid.
g was added little by little. As the carboxylic acid reacted, carbon dioxide gas bubbles were generated violently.
１．５時間かけてカルボン酸を添加した後、反応液を約
４０℃の水浴で３０分加熱してカルボン酸の結晶を完全
に溶かした。この溶液に硫酸ジメチル１９−を５分で滴
下し、混合物を５０℃で４０分反応させた。After adding the carboxylic acid over 1.5 hours, the reaction solution was heated in a water bath at about 40° C. for 30 minutes to completely dissolve the carboxylic acid crystals. Dimethyl sulfate 19- was added dropwise to this solution over 5 minutes, and the mixture was reacted at 50°C for 40 minutes.
次に、炭酸ナトリウムｌ１ｇ 、続いて硫酸ジメチル１
９−を添加して４０分同温度で反応させた後、更に、炭
酸ナトリウム５．５ｇと硫酸ジメチルｌ〇−を順次加え
、１時間攪拌して反応を終了させた。反応混合物を室温
に下げ、析出した白色沈澱物を吸引濾過し水洗して乾燥
した。このようにして得たものを、ジオキサンより再結
晶して精製すると、ナフタレン−１，４，５，８−テト
ラカルボン酸テトラメチルエステルが無色結晶として得
られた（１５．０ｇ、収率８４％）。Then 1 g of sodium carbonate followed by 1 g of dimethyl sulfate
After adding 9- and reacting at the same temperature for 40 minutes, 5.5 g of sodium carbonate and dimethyl sulfate 10- were sequentially added and stirred for 1 hour to complete the reaction. The reaction mixture was cooled to room temperature, and the precipitated white precipitate was suction filtered, washed with water, and dried. The product thus obtained was purified by recrystallization from dioxane, and naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester was obtained as colorless crystals (15.0 g, yield 84%). ).
ｍ、ｐ、１９８−１９９℃。m, p, 198-199°C.
元素分析：測定値Ｃ；６０．２１． Ｈ：４．５０計算
値ｃ；６ｏ、ｏｏ、 Ｈ；４．４８（ＣｔａＨｔｈＯａ
）高分解能質量分析：測定値３６０．０７８（計算値３
６０．０８５）実施例２
水素化ジイソブチルアルミニウム１モルを含むヘキサン
１０１００Ｏの攪拌溶液に、ナフタレン−１，４，５，
８−テトラカルボン酸テトラメチルエステル２５ｇの結
晶を少しずつ添加した。Elemental analysis: Measured value C; 60.21. H: 4.50 Calculated value c; 6o, oo, H; 4.48 (CtaHthOa
) High-resolution mass spectrometry: Measured value 360.078 (calculated value 3
60.085) Example 2 Naphthalene-1,4,5,
25 g of crystals of 8-tetracarboxylic acid tetramethyl ester were added in portions.
発熱により反応液が室温を越えないように、時々反応フ
ラスコを氷水浴で冷却した。エステルは添加と共にすみ
やかに溶解し透明な反応液が得られた。添加終了後、反
応液を更に８日間室温で攪拌した。反応混合物に、冷却
下、メタノール、水、希塩酸の順で添加して過剰の水素
化物を分解し、更に水を加えて室温で攪拌した。The reaction flask was occasionally cooled in an ice-water bath to prevent the reaction solution from exceeding room temperature due to exotherm. The ester dissolved immediately upon addition, and a transparent reaction solution was obtained. After the addition was complete, the reaction was stirred for an additional 8 days at room temperature. Methanol, water, and dilute hydrochloric acid were sequentially added to the reaction mixture under cooling to decompose excess hydride, and water was further added and the mixture was stirred at room temperature.
生じた白色固体を吸引濾過して集め、充分水洗して乾燥
後、ジメチルスルホキシド−クロロホルムの混合溶媒か
ら再結晶すると、１．４．５．８−テトラキス（ヒドロ
キシメチル）ナフタレンが無色微結晶として得られた（
１６．２ｇ、収率９４％）。The resulting white solid was collected by suction filtration, thoroughly washed with water, dried, and then recrystallized from a mixed solvent of dimethyl sulfoxide and chloroform to obtain 1.4.5.8-tetrakis(hydroxymethyl)naphthalene as colorless microcrystals. (
16.2 g, yield 94%).
ｍ、ｐ、２２９−２３１℃。m, p, 229-231°C.
元素分析：測定値Ｃ：６７．８５． Ｈ；６．３８計算
値Ｃ；６７．７３． Ｈ：６．５０（Ｃｔ４Ｈい０４）
高分解能質量分析：測定値２４８．０９６（計算値２４
８．１０５）実施例３
１．４，５．８−テトラキス（ヒドロキシメチル）ナフ
タレン０．１ｇ、無水酢酸４−およびピリジン４−の混
合物を攪拌しながら６０〜７０℃の水浴で加熱した。２
０分後、原料のテトラオールの結晶が完全に消失した時
点で水浴を除き、反応混合物を室温に放置した。Elemental analysis: Measured value C: 67.85. H; 6.38 Calculated value C; 67.73. H:6.50 (Ct4H04)
High-resolution mass spectrometry: Measured value 248.096 (calculated value 24
8.105) Example 3 A mixture of 0.1 g of 1.4,5.8-tetrakis(hydroxymethyl)naphthalene, 4-acetic anhydride and 4-pyridine was heated with stirring in a water bath at 60-70°C. 2
After 0 minutes, when the raw material tetraol crystals completely disappeared, the water bath was removed and the reaction mixture was left at room temperature.
８日後、生じた薄茶色溶液を氷−希塩酸中にあけ、水を
加えて室温で攪拌した。析出した固体を吸引濾過して集
め水洗して乾燥した。このようにして得たものをエタノ
ールから再結晶して精製すると、１，４．５．８−テト
ラキス（アセトキシメチル）ナフタレンが無色微結晶と
して得られた（０．１３ｇ、収率７６％）。After 8 days, the resulting light brown solution was poured into ice-diluted hydrochloric acid, water was added, and the mixture was stirred at room temperature. The precipitated solid was collected by suction filtration, washed with water, and dried. When the product thus obtained was purified by recrystallization from ethanol, 1,4.5.8-tetrakis(acetoxymethyl)naphthalene was obtained as colorless microcrystals (0.13 g, yield 76%).
ｍ、ｐ、１７２−１７３℃。m, p, 172-173°C.
元素分析：測定値Ｃ：６３．６１． Ｈ；５．９５計算
値Ｃ：６３．４５． Ｈ；５．８１（Ｃｚ□Ｈ！４０８
）実施例４
純度約６０％の水素化ナトリウム−オイル混合物０．３
ｇをペンタンでよく洗い充分オイルを除いた後、テトラ
ヒドロフラン８０−を加えた。この水素化ナトリウム−
テトラヒドロフラン懸濁液に１．４．５．８−テトラキ
ス（ヒドロキシメチル）ナフタレン０．２５ｇを加え、
混合物をよく攪拌しながら６時間加熱還流した０次に、
４５℃で１５時間攪拌後、反応温度を３５℃に下げ、ヨ
ウ化メチル２ＷＩｌを添加した。２時間後、更にヨウ化
メチル２−を加え、３５℃で２時間反応させた後、更に
５時間還流した０反応温度を再び３５℃に下げ、更にヨ
ウ化メチル４ｄを加え、１６時間攪拌して反応を終了さ
せた。反応混合物を約３分の１に濃縮して水を加え、生
じた白色沈澱物を吸引濾過して集めた。このようにして
得たものをヘキサンから再結晶して精製すると、１．４
．５．８−テトラキス（メトキシメチル）ナフタレンが
無色微結晶として得られた（０．２０ｇ、収率６６％）
。Elemental analysis: Measured value C: 63.61. H: 5.95 Calculated value C: 63.45. H; 5.81 (Cz□H!408
) Example 4 Sodium hydride-oil mixture with a purity of about 60% 0.3
After thorough washing with pentane to remove oil, 80% of tetrahydrofuran was added. This sodium hydride
Add 0.25 g of 1.4.5.8-tetrakis(hydroxymethyl)naphthalene to the tetrahydrofuran suspension,
The mixture was heated to reflux for 6 hours with good stirring.
After stirring at 45°C for 15 hours, the reaction temperature was lowered to 35°C and 2WIl of methyl iodide was added. After 2 hours, methyl iodide 2- was further added, and the mixture was reacted at 35°C for 2 hours, and then refluxed for another 5 hours.The reaction temperature was lowered to 35°C again, and methyl iodide 4d was further added, and the mixture was stirred for 16 hours. The reaction was terminated. The reaction mixture was concentrated to about one third, water was added and the resulting white precipitate was collected by suction filtration. When the product obtained in this way is purified by recrystallization from hexane, the result is 1.4
．． 5.8-tetrakis(methoxymethyl)naphthalene was obtained as colorless microcrystals (0.20 g, yield 66%).
.
ｍ、ｐ、１１９−１２０℃。m, p, 119-120°C.
元素分析：測定値Ｃ；７１．００． ）Ｉ；７．８０計
算値Ｃ；７１．０２． Ｈ；７．９５（Ｃ＋ａＨｚａＯ
ｎ）質量分析：測定値３０４（計算値３０４）〔発明の
効果〕
以上述べたように本発明によれば、ナフタレン−１，４
，５，８−テトラカルボン酸テトラアルキルエステルを
、ナフタレン−１，４，５，８−テトラカルボン酸から
従来の製造方法で使用した銀塩やヨウ化メチルに比較し
て安価なアルカリ金属炭酸塩や硫酸ジアルキルを用いて
高収率で製造することができる。しかも本発明の製造方
法は、大量生産が可能である。Elemental analysis: Measured value C; 71.00. ) I; 7.80 Calculated value C; 71.02. H; 7.95 (C+aHzaO
n) Mass spectrometry: Measured value 304 (calculated value 304) [Effects of the invention] As described above, according to the present invention, naphthalene-1,4
, 5,8-tetracarboxylic acid tetraalkyl ester from naphthalene-1,4,5,8-tetracarboxylic acid using an alkali metal carbonate that is cheaper than the silver salt or methyl iodide used in the conventional manufacturing method. It can be produced in high yield using dialkyl sulfate or dialkyl sulfate. Furthermore, the manufacturing method of the present invention allows mass production.
従って本発明によれば、ナフタレン−１，４，５゜８−
テトラカルボン酸テトラアルキルエステルを安価に、大
規模に供給することができる。得られたテトラアルキル
エステルは、ポリエステルやポリアミド製造用のモノマ
ーとして有用である。According to the invention, therefore, naphthalene-1,4,5°8-
Tetracarboxylic acid tetraalkyl ester can be supplied inexpensively and on a large scale. The obtained tetraalkyl ester is useful as a monomer for producing polyesters and polyamides.
また本発明によれば、新規化合物として、■。Moreover, according to the present invention, as a new compound, ■.
４．５．８−テトラキス （ヒドロキシメチル）ナフタ
レン、１，４．５．８−テトラキス（ヒドロキシメチル
）ナフタレンテトラエーテルおよび１．４．５゜８−テ
トラキス（アシルオキシメチル）ナフタレンが得られる
。4.5.8-tetrakis(hydroxymethyl)naphthalene, 1,4.5.8-tetrakis(hydroxymethyl)naphthalenetetraether and 1.4.5°8-tetrakis(acyloxymethyl)naphthalene are obtained.
かかる化合物も、ポリエステルやポリエーテル用モノマ
ーとして有用であり、また界面活性剤製造原料としても
有用である。Such compounds are also useful as monomers for polyesters and polyethers, and are also useful as raw materials for producing surfactants.
かつ、かかる化合物は、ナフタレン１．４．５．８−テ
トラカルボン酸テトラアルキルエステルから容易に製造
することができる。Moreover, such a compound can be easily produced from naphthalene 1,4,5,8-tetracarboxylic acid tetraalkyl ester.
Claims (1)
テトラアルカリ金属塩に硫酸ジアルキルを作用させるこ
とを特徴とする下記一般式（ I ）で示されるナフタレ
ン−１，４，５，８−テトラカルボン酸テトラアルキル
エステルの製造方法。 ▲数式、化学式、表等があります▼（ I ） ただし、（ I ）式中、Ｒ＾１はＣ＿１〜Ｃ＿２のアル
キル基である。 ２、下記構造式（１）で示される１，４，５，８−テト
ラキス（ヒドロキシメチル）ナフタレン。 ▲数式、化学式、表等があります▼（１） ３、下記一般式（II）で示される１，４，５，８−テト
ラキス（ヒドロキシメチル）ナフタレン誘導体。 ▲数式、化学式、表等があります▼（II） ただし（II）式中、ＯＲ＾２はアルコール残基またはカ
ルボン酸残基である。 ４、下記一般式（ I ）で示される１，４，５，８−テ
トラカルボン酸テトラアルキルエステルを水素化ジアル
キルアルミニウムで還元することを特徴とする下記構造
式（１）で示される １，４，５，８−テトラキス（ヒドロキシメチル）ナフ
タレンの製造方法。 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（１） ただし（ I ）式中、Ｒ＾１はＣ＿１〜Ｃ＿２のアルキ
ル基である。 ５、下記構造式（１）で示される１，４，５，８−テト
ラキス（ヒドロキシメチル）ナフタレンをエーテル化剤
またはエステル化剤で処理することを特徴とする下記一
般式（II）で示される１，４，５，８−テトラキス（ヒ
ドロキシメチル）ナフタリン誘導体の製造方法。 ▲数式、化学式、表等があります▼（１） ▲数式、化学式、表等があります▼（II） ただし（II）式中、ＯＲ＾２はアルコール残基またはカ
ルボン酸残基である。[Scope of Claims] 1. Naphthalene-1 represented by the following general formula (I), which is obtained by reacting a tetraalkali metal salt of naphthalene-1,4,5,8-tetracarboxylic acid with a dialkyl sulfate; A method for producing 4,5,8-tetracarboxylic acid tetraalkyl ester. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, in the formula (I), R^1 is an alkyl group of C_1 to C_2. 2. 1,4,5,8-tetrakis(hydroxymethyl)naphthalene represented by the following structural formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) 3. 1,4,5,8-tetrakis(hydroxymethyl)naphthalene derivative represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) However, in formula (II), OR^2 is an alcohol residue or a carboxylic acid residue. 4. 1,4 represented by the following structural formula (1), which is characterized by reducing the 1,4,5,8-tetracarboxylic acid tetraalkyl ester represented by the following general formula (I) with dialkyl aluminum hydride. , 5,8-tetrakis(hydroxymethyl)naphthalene production method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) However, in the formula (I), R^1 is an alkyl group of C_1 to C_2. 5. A product represented by the following general formula (II) characterized by treating 1,4,5,8-tetrakis(hydroxymethyl)naphthalene represented by the following structural formula (1) with an etherifying agent or an esterifying agent. A method for producing a 1,4,5,8-tetrakis(hydroxymethyl)naphthalene derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) However, in formula (II), OR^2 is an alcohol residue or a carboxylic acid residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6687688A JPH01238548A (en) | 1988-03-18 | 1988-03-18 | 1,4,5,8-tetrakis(hydroxymethyl)naphthalene, its derivative and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6687688A JPH01238548A (en) | 1988-03-18 | 1988-03-18 | 1,4,5,8-tetrakis(hydroxymethyl)naphthalene, its derivative and production thereof |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4238990A Division JPH082821B2 (en) | 1992-08-14 | 1992-08-14 | 1,4,5,8-Tetrakis (hydroxymethyl) naphthalene derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01238548A true JPH01238548A (en) | 1989-09-22 |
| JPH0513938B2 JPH0513938B2 (en) | 1993-02-23 |
Family
ID=13328514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6687688A Granted JPH01238548A (en) | 1988-03-18 | 1988-03-18 | 1,4,5,8-tetrakis(hydroxymethyl)naphthalene, its derivative and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01238548A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5800995A (en) * | 1984-03-29 | 1998-09-01 | Li-Cor, Inc. | Sequencing near infrared and infrared fluorescence labeled DNA for detecting using laser diodes and suitable labels therefor |
| CN109942430A (en) * | 2019-03-26 | 2019-06-28 | 宝鸡文理学院 | Naphthalene tetracarboxylic acid ester type compound and preparation method thereof and application as lubricating oil |
-
1988
- 1988-03-18 JP JP6687688A patent/JPH01238548A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| JOURNAL OF ORGANIC CHEMISTRY=1982 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5800995A (en) * | 1984-03-29 | 1998-09-01 | Li-Cor, Inc. | Sequencing near infrared and infrared fluorescence labeled DNA for detecting using laser diodes and suitable labels therefor |
| CN109942430A (en) * | 2019-03-26 | 2019-06-28 | 宝鸡文理学院 | Naphthalene tetracarboxylic acid ester type compound and preparation method thereof and application as lubricating oil |
| CN109942430B (en) * | 2019-03-26 | 2021-08-10 | 宝鸡文理学院 | Naphthalene tetracarboxylic ester compound, preparation method thereof and application thereof as lubricating oil |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0513938B2 (en) | 1993-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20010053294A (en) | Method for producing ortho-alkylated benzoic acid derivatives | |
| US4144397A (en) | Preparation of 2-aryl-propionic acids by direct coupling utilizing a mixed magnesium halide complex | |
| JPH082821B2 (en) | 1,4,5,8-Tetrakis (hydroxymethyl) naphthalene derivative and method for producing the same | |
| JPH02188570A (en) | Production of halogen-substituted quinoline derivative | |
| JPH01238548A (en) | 1,4,5,8-tetrakis(hydroxymethyl)naphthalene, its derivative and production thereof | |
| SU581860A3 (en) | Method of preparing acyl derivatives of dianhydrohexitols | |
| JPH0610158B2 (en) | Method for producing 3-fluorobenzoic acids | |
| JPS6053039B2 (en) | N-Acetyl/Iramic acid derivative and method for producing the same | |
| JPH07206816A (en) | Preparation of 2,4,5-tribromopyrrole-3-carbonitrile | |
| JPH03141294A (en) | Production of 21-desoxyprednisolone-17-ester | |
| US3622619A (en) | Biphenyl compounds | |
| US4031136A (en) | Process for the preparation of trans, trans-muconic acid | |
| KR940006531B1 (en) | Process for preparation of pyridine derivatives | |
| JPS60105645A (en) | Production of arylsuccinic acid ester | |
| JP2500316B2 (en) | 1,4,5,8-Tetrakis (halogenomethyl) naphthalene derivative and method for producing the same | |
| JPS6127396B2 (en) | ||
| JPH0128013B2 (en) | ||
| JPS5916878A (en) | Production of 2,4-dihydroxy-3-acetylquinoline | |
| JPH0460591B2 (en) | ||
| US4451658A (en) | Process for producing substituted pyrroles | |
| JPS59163370A (en) | Preparation of 0-(aminomethyl)phenylacetic lactam | |
| JPS6191163A (en) | Preparation of anthranylic acid derivative | |
| JPS62273950A (en) | 4-alkoxy-3-pyrroline-2-one-1-yl-acetic acid amide, manufacture and use | |
| JPS58216159A (en) | Production of quinoline derivative | |
| JPS5934190B2 (en) | Method for producing 3,5↓-dimethyl↓-4↓-lower alkoxycarbonyl phthalic anhydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |