JPH01216952A - Novel 2-(1-alakylaminoalkyl)-3-hydroxy-1,4-naphthoquinone, production thereof and production of 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinone - Google Patents
Novel 2-(1-alakylaminoalkyl)-3-hydroxy-1,4-naphthoquinone, production thereof and production of 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinoneInfo
- Publication number
- JPH01216952A JPH01216952A JP63041755A JP4175588A JPH01216952A JP H01216952 A JPH01216952 A JP H01216952A JP 63041755 A JP63041755 A JP 63041755A JP 4175588 A JP4175588 A JP 4175588A JP H01216952 A JPH01216952 A JP H01216952A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxy
- naphthoquinone
- mmol
- reaction
- alkenyl
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 29
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims 1
- CSFWPUWCSPOLJW-UHFFFAOYSA-N hydroxynaphthoquinone Natural products C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 abstract description 35
- 150000001875 compounds Chemical class 0.000 abstract description 12
- -1 aliphatic aldehyde Chemical class 0.000 abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 2
- WVCHIGAIXREVNS-UHFFFAOYSA-N 2-hydroxy-1,4-naphthoquinone Chemical compound C1=CC=C2C(O)=CC(=O)C(=O)C2=C1 WVCHIGAIXREVNS-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000013078 crystal Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- 229930192627 Naphthoquinone Natural products 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- YLVFKSGFPRCBPI-UHFFFAOYSA-N C1=CC=C2C(=O)C(C=CCCCCCCCCCC)=C(O)C(=O)C2=C1 Chemical compound C1=CC=C2C(=O)C(C=CCCCCCCCCCC)=C(O)C(=O)C2=C1 YLVFKSGFPRCBPI-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000002791 naphthoquinones Chemical class 0.000 description 4
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KJKMZQXHACNTFZ-UHFFFAOYSA-N C1=CC=C2C(=O)C(C(NC)CCCCCCCCCCC)=C(O)C(=O)C2=C1 Chemical compound C1=CC=C2C(=O)C(C(NC)CCCCCCCCCCC)=C(O)C(=O)C2=C1 KJKMZQXHACNTFZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- BGEHHAVMRVXCGR-UHFFFAOYSA-N methylundecylketone Natural products CCCCCCCCCCCCC=O BGEHHAVMRVXCGR-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- IKLBQSHCLSCPNX-UHFFFAOYSA-N C1=CC=C2C(=O)C(C(CCC)NCCCC)=C(O)C(=O)C2=C1 Chemical compound C1=CC=C2C(=O)C(C(CCC)NCCCC)=C(O)C(=O)C2=C1 IKLBQSHCLSCPNX-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- PIYDVAYKYBWPPY-UHFFFAOYSA-N heptadecanal Chemical compound CCCCCCCCCCCCCCCCC=O PIYDVAYKYBWPPY-UHFFFAOYSA-N 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- FWWQKRXKHIRPJY-UHFFFAOYSA-N octadecanal Chemical compound CCCCCCCCCCCCCCCCCC=O FWWQKRXKHIRPJY-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- UHUFTBALEZWWIH-UHFFFAOYSA-N tetradecanal Chemical compound CCCCCCCCCCCCCC=O UHUFTBALEZWWIH-UHFFFAOYSA-N 0.000 description 2
- KMPQYAYAQWNLME-UHFFFAOYSA-N undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NMDFGILPGQYSNB-UHFFFAOYSA-N C1=CC=C2C(=O)C(C(CC(C)C)NC)=C(O)C(=O)C2=C1 Chemical group C1=CC=C2C(=O)C(C(CC(C)C)NC)=C(O)C(=O)C2=C1 NMDFGILPGQYSNB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000078 anti-malarial effect Effects 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940091170 naphthoquine Drugs 0.000 description 1
- XGQJZNCFDLXSIJ-UHFFFAOYSA-N pentadecanal Chemical compound CCCCCCCCCCCCCCC=O XGQJZNCFDLXSIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用性1
本発明は医薬や農薬の中間体として有用な、新規な2−
(1−アルキルアミノアルキル)−3−ヒドロキシ−1
,4−ナフトキノン及びその製造方法、並びに該新規化
合物を用いて2−(1−アルケニル)−3−ヒドロキシ
−1,4−ナフトキノンを製造する方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Industrial Applicability 1] The present invention provides novel 2-
(1-alkylaminoalkyl)-3-hydroxy-1
, 4-naphthoquinone, a method for producing the same, and a method for producing 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinone using the novel compound.
2−(1−アルケニル)−3−ヒドロキシ−1,4−ナ
フトキノンは殺虫活性及び殺菌活性を有する化合物であ
り、またアルケニル基を水素化して得られる2−フルキ
ル−3−ヒドロキシ−1,4−ナフトキノンは医薬、動
物薬及び農薬として有用である。2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinone is a compound with insecticidal and bactericidal activity, and 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinone is a compound obtained by hydrogenating an alkenyl group. Naphthoquinones are useful as pharmaceuticals, veterinary drugs, and pesticides.
[従来の技術]
従来より、2−フルキルアミノメチル−3−ヒドロキシ
−1,4−ナフトキノンは、2−ヒドロキシ1.4−ナ
フトキノンとホルマリン及び第−級若しくは第二級アミ
ンを反応させることで容易に得られる事が知られており
[M、T、Lef目er and R1,Hatbaw
ay:J、 Amer、 Chew、 Soc、、 Z
L、 3222(1948)]、また。[Prior Art] Conventionally, 2-fulkylaminomethyl-3-hydroxy-1,4-naphthoquinone is produced by reacting 2-hydroxy 1,4-naphthoquinone with formalin and a primary or secondary amine. It is known that it can be easily obtained [M, T, Lef and R1, Hatbaw
ay:J, Amer, Chew, Soc,, Z
L., 3222 (1948)], also.
ベンズアルデヒドやアセトアルデヒドと反応して、それ
ぞれ2−(l−アルキルアミノベンジル)−3−ヒドロ
キシ−1,4−ナフトキンあるいは2−(l−アルキル
アミンエチル)−3−ヒドロキシ−1,4−ナフトキノ
ンを与える本が知られている[C,E、Dalglie
sh:J、 Amer、 Chew、 SQC,、LL
107(1944)Lそして、更にこれらの化合物が
抗マラリア活性を有することについても調べられている
EL、F、Freser及び A、R,Richard
son: J、 AIIer、 Chew、
SOc、、 70゜3158(1948)] 。Reacts with benzaldehyde or acetaldehyde to give 2-(l-alkylaminobenzyl)-3-hydroxy-1,4-naphthoquine or 2-(l-alkylaminoethyl)-3-hydroxy-1,4-naphthoquinone, respectively. The book is known [C, E, Dalglie
sh:J, Amer, Chew, SQC,,LL
107 (1944) and furthermore these compounds have also been investigated for their antimalarial activity. EL, F. Freser and A. R. Richard.
son: J, AIIer, Chew,
SOc, 70°3158 (1948)].
一方、2−(l−アルケニル)−3−ヒドロキシ−1,
4−ナフトキノンの製造法としては、
■ 2−ヒドロキシ−1,4−ナフトキノンとその数モ
ル倍量のアルデヒドとを酢酸溶媒中で、約1.7モル倍
量の塩酸を触媒として脱水縮合させて製造する方法[J
、 Am、 Chew、 Sac、、 5B、 pH8
3〜11f17(11136)ゴまたは
■ 上記■の方法において、触媒として塩酸の代わりに
トリエチルアミンを、また溶媒としてジメチルホルムア
ミド又はアセトニトリルを使用する方法[J、 Che
w、 Sac、 Perkin Trans、 I、
p85fJ〜884(In2)]
が知られているのみである。On the other hand, 2-(l-alkenyl)-3-hydroxy-1,
The method for producing 4-naphthoquinone is as follows: (1) 2-hydroxy-1,4-naphthoquinone and several moles of aldehyde are dehydrated and condensed in an acetic acid solvent using about 1.7 moles of hydrochloric acid as a catalyst. Method of manufacturing [J
, Am, Chew, Sac, 5B, pH8
3-11f17 (11136) Go or ■ A method of using triethylamine instead of hydrochloric acid as a catalyst and dimethylformamide or acetonitrile as a solvent in the method of ■ above [J, Che
w, Sac, Perkin Trans, I,
p85fJ~884(In2)] is only known.
[発明が解決しようとする課題]
しかしながら、2−(1−アルキルアミノアルキル)−
3−ヒドロキシ−1,4−ナフトキノンの製造に関する
これらの報告では、ホルマリン、ベンズアルデヒド、ア
セトアルデヒド以外のアルデヒドを用いた場合には、こ
の反応はうまく進行せず、タール状物質が得られるか、
もしくは2.2゛−メチレンビス−3−ヒドロキシ−1
,4−ナフトキノン誘導体が生成するのみで、01以上
の脂肪族アルデヒドを用いた場合は2−(1−アルキル
アミノアルキル)−3−ヒドロキシ−1,4−ナフトキ
ノンは得られないと報告されており、この反応の応用範
囲が限られたものとなっていた。[Problem to be solved by the invention] However, 2-(1-alkylaminoalkyl)-
In these reports regarding the production of 3-hydroxy-1,4-naphthoquinone, it was found that when aldehydes other than formalin, benzaldehyde, and acetaldehyde are used, the reaction does not proceed well and a tar-like substance is obtained, or
or 2.2゛-methylenebis-3-hydroxy-1
It has been reported that only ,4-naphthoquinone derivatives are produced, and that 2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone cannot be obtained when an aliphatic aldehyde of 01 or higher is used. However, the scope of application of this reaction was limited.
また、2−(トアルケニル)−3−ヒドロキシ−1,4
−ナフトキノンの製造法として前記の塩酸を触媒として
用いる方法は、塩酸が極めて腐食性の強い酸であるため
、装置材料が特殊となり、工°業的な製造方法としては
実用的であるとはいえない、また、これらの方法はいず
れも収率が約30〜40モル2程度であり、しかも大過
剰のアルデヒドを使用するために、アルデヒドの縮合物
やその他の副生成物が大量に生成し、目的物の単離方法
が煩雑になるなどの欠点があり、工業的に有利な方法と
はいえない、なお、前記■の方法は汎用性があるとはい
えず、大半の場合が2,2°−メチレンビス−3−ヒド
ロキシ−1,4−ナフトキノン誘導体の生成が優先して
しまう。Also, 2-(toalkenyl)-3-hydroxy-1,4
-The above-mentioned method for producing naphthoquinone using hydrochloric acid as a catalyst requires special equipment materials because hydrochloric acid is an extremely corrosive acid, and although it is not practical as an industrial production method. In addition, in all of these methods, the yield is about 30 to 40 moles, and since a large excess of aldehyde is used, a large amount of aldehyde condensates and other by-products are produced. It has drawbacks such as the complicated method of isolating the target product, so it cannot be said to be an industrially advantageous method.In addition, the method (2) above cannot be said to be versatile, and in most cases Preference is given to the production of °-methylenebis-3-hydroxy-1,4-naphthoquinone derivatives.
[課題を解決するための手段]
本発明者らは、2−(1−アルキルアミノアルキル)−
3−ヒドロキシ−1,4−ナフトキノンの製造方法につ
いて、鋭意検討した結果、ホルマリン、ベンズアルデヒ
ド、アセトアルデヒド以外の種々のアルデヒドに対して
も、第一級アミン及び特定の溶媒を使用し、さらに反応
温度を35℃以下に保つことによって、従来得られなか
った新規な2−(1−アルキルアミノアルキル)−3−
ヒドロキシ−1,4−ナフトキノンを選択的に高収率で
得られること、また、使用する溶媒によっては生成物を
結晶としてそのまま容易に単離できることを見出し本発
明を完成した。[Means for solving the problem] The present inventors have discovered that 2-(1-alkylaminoalkyl)-
As a result of extensive research into the production method of 3-hydroxy-1,4-naphthoquinone, we found that a primary amine and a specific solvent were used for various aldehydes other than formalin, benzaldehyde, and acetaldehyde, and the reaction temperature was increased. By keeping the temperature below 35°C, a new 2-(1-alkylaminoalkyl)-3-
The present invention was completed by discovering that hydroxy-1,4-naphthoquinone can be selectively obtained in high yield, and that depending on the solvent used, the product can be easily isolated as crystals.
また、2−(1−フルケニル)−3−ヒドロキシ−1,
4−ナフトキノンの製造に関しても、以上の方法により
製造した2−(トアルキルアミノアルキル)−3−ヒド
ロキシ−1,4−ナフトキノンを不活性な有機溶媒中で
硫酸、ハロゲン化水素酸などの酸の存在下で熱分解反応
を行なうことにより、収串良< 2−(1−フルケニル
)−3−ヒドロキシ−1,4−ナフトキノンを製造でき
ることを見出した。Also, 2-(1-fulkenyl)-3-hydroxy-1,
Regarding the production of 4-naphthoquinone, the 2-(toalkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone produced by the above method was treated with an acid such as sulfuric acid or hydrohalic acid in an inert organic solvent. It has been found that 2-(1-flukenyl)-3-hydroxy-1,4-naphthoquinone can be produced by carrying out a thermal decomposition reaction in the presence of 2-(1-flukenyl)-3-hydroxy-1,4-naphthoquinone.
すなわち本発明は、
一般式
(式中 R1はアルキル基又はシクロアルキル基を R
2は炭素数2以上のアルキル基を示す、)
で表される新規な2−(1−アルキルアミノアルキル)
−3−ヒドロキシ−1,4−ナフトキノンを提供するも
のである。That is, the present invention is based on the general formula (wherein R1 represents an alkyl group or a cycloalkyl group)
A novel 2-(1-alkylaminoalkyl) represented by 2 represents an alkyl group having 2 or more carbon atoms.
-3-hydroxy-1,4-naphthoquinone.
本発明の上記新規ナフトキノン化合物は、2−ヒドロキ
シ−1,4−ナフトキノン(A)と炭素数が3以上の脂
肪族アルデヒド(B)とを、第一級アミン(C)の存在
下に不活性有機溶媒中で反応させることにより得られる
。The novel naphthoquinone compound of the present invention comprises inactivating 2-hydroxy-1,4-naphthoquinone (A) and an aliphatic aldehyde having 3 or more carbon atoms (B) in the presence of a primary amine (C). Obtained by reaction in an organic solvent.
上記方法により、2−(1−アルキルアミノアルキル)
−3−ヒドロキシ−1,4−ナフトキノン(D)を得る
反応は次の反応式によって表わされる。By the above method, 2-(1-alkylaminoalkyl)
The reaction to obtain -3-hydroxy-1,4-naphthoquinone (D) is represented by the following reaction formula.
本発明に用いられるアルデヒドとしては、炭素数が3以
上のアルデヒドR2CHOが使用される。As the aldehyde used in the present invention, an aldehyde R2CHO having 3 or more carbon atoms is used.
ここでR2は炭素数が2以上、好ましくは5〜20のア
ルキル基を表わし、上記目的化合物(D)のR2に応じ
て選ばれる。Here, R2 represents an alkyl group having 2 or more carbon atoms, preferably 5 to 20 carbon atoms, and is selected depending on R2 of the target compound (D).
主要なアルデヒドとしては1例えばプロピオンアルデヒ
ド、ブチルアルデヒド、イソブチルアルデヒド、バレル
アルデヒド、イソバレルアルデヒド、ピバリンアルデヒ
ド、カプロンアルデヒド。The principal aldehydes are, for example, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, pivalaldehyde, capronaldehyde.
ヘプチルアルデヒド、カプリルアルデヒド、ペラルゴン
アルデヒド、カプリンアルデヒド、ウンデシルアルデヒ
ド、ドデシルアルデヒド(ラウリンアルデヒド)、トリ
デシルアルデヒド、ミリスチンアルデシド、ペンタデシ
ルアルデヒド、マルガリンアルデヒド、ステアリルアル
デヒドなどの脂肪族飽和アルデヒドが挙げられる。Aliphatic saturated aldehydes such as heptylaldehyde, caprylicaldehyde, pelargonaldehyde, capricaldehyde, undecylaldehyde, dodecylaldehyde (lauric aldehyde), tridecylaldehyde, myristicaldehyde, pentadecylaldehyde, margaric aldehyde, stearyl aldehyde, etc. .
該アルデヒドの使用量は、原料の2−ヒドロキシ−1,
4−ナフトキノンに対して一般に等モル以上1通常1.
0〜2.0モル倍、好ましくは1.1〜1.4モル倍で
あり9等モル未満では収率が低下し、多くても経済的で
ない。The amount of the aldehyde used is based on the raw material 2-hydroxy-1,
Generally 1 or more moles per 4-naphthoquinone, usually 1.
The amount is 0 to 2.0 times by mole, preferably 1.1 to 1.4 times by mole, and if it is less than 9 equivalent moles, the yield will decrease and even at most it is not economical.
上記反応に用いられるアミンRI NR2はアルキルア
ミンまたはシクロアルキルアミン等の第一級アミンに限
られる。第二級アミン、第三級アミンでは、2.2°−
メチレンビス−3−ヒドロキシ−1,4−ナツトキノン
誘導体の生成が優先する。このアミンはガス状でも液状
でもよく、また、水溶液でもよい、RIもまた目的化合
物(D)のRIに応じて選ばれる。一般にはモノメチル
アミン、エチルアミン、n−プロピルアミン、i−プロ
ピルアミン、ブチルアミン、t−ブチルアミン等の第一
級アルキルアミンまたはシクロヘキシルアミン等のシク
ロアルキル7ミドが挙げられる。The amine RI NR2 used in the above reaction is limited to primary amines such as alkyl amines or cycloalkylamines. For secondary amines and tertiary amines, 2.2°-
Preference is given to the formation of methylenebis-3-hydroxy-1,4-nattoquinone derivatives. This amine may be in gaseous or liquid form, or may be in an aqueous solution, and the RI is also selected depending on the RI of the target compound (D). Generally, primary alkyl amines such as monomethylamine, ethylamine, n-propylamine, i-propylamine, butylamine, t-butylamine, or cycloalkyl 7amides such as cyclohexylamine are mentioned.
第一級アミンの使用量は、原料の2−ヒドロキシ−1,
4−ナフトキノンに対して、一般に0.8〜1.5モル
倍、好ましくは0.3〜1.1モル倍、更に好ましくは
等モル倍である。アミンの使用量は多くても少なくても
目的化合物の収率が低下する。The amount of primary amine used is 2-hydroxy-1,
The amount is generally 0.8 to 1.5 moles, preferably 0.3 to 1.1 moles, and more preferably equimolar to 4-naphthoquinone. Whether the amount of amine used is large or small, the yield of the target compound decreases.
前記反応に用いられる不活性有機溶媒としては1例えば
アルコール、セロソルブ、ニー、チル(ジオキサン、
THF)、ジオール、ケトン、脂肪酸エステル、芳香族
炭化水素(B、T、X、)アセトニトリル等が用いられ
、目的物を結晶として容易に単離する場合には1通常、
メタノール、エタノール等のアルコール類が好都合であ
る。Examples of the inert organic solvent used in the reaction include alcohol, cellosolve, dioxane,
(THF), diols, ketones, fatty acid esters, aromatic hydrocarbons (B, T,
Alcohols such as methanol, ethanol and the like are convenient.
上記反応の反応条件としては、反応温度が35℃以下で
ある事が望ましく、好ましくは0〜30℃。Regarding the reaction conditions for the above reaction, it is desirable that the reaction temperature is 35°C or lower, preferably 0 to 30°C.
特に好ましくは20〜25℃である。温度が高すぎると
2.2°−メチルビス−3−ヒドロキシ−1,4−ナ
フトキノン誘導体の生成が優先し、低すぎると反応速度
が非常に遅くなり実用的でない0反応時間は 1〜10
時間程時間光分である。Particularly preferably, the temperature is 20 to 25°C. If the temperature is too high, the production of the 2.2°-methylbis-3-hydroxy-1,4-naphthoquinone derivative takes priority, and if the temperature is too low, the reaction rate becomes extremely slow and the reaction time is 1 to 10, which is not practical.
Hours are hours and minutes of light.
本発明における上記製造方法は一般に次の様に実施され
る。The above manufacturing method according to the present invention is generally carried out as follows.
所定量の2−ヒドロキシ−1,4−ナフトキノンと、第
一級アミンとを、所定量の溶媒中に加え、2−ヒドロキ
シ−1,4−ナフトキノンの第一級アミン塩を生成させ
た後に、さらに所定量のアルデヒドを添加し、攪拌下に
所定温度で1−10時間反応させるか、あるいは所定量
の第一級アミンとアルデヒドとを、所定量の溶媒中に加
え、シッフ塩基を生成させた後に、さらに所定量の2−
ヒドロキシ−1,トナフトキノンを添加し、攪拌下に所
定温度で 1〜10時間反応させる。析出してきた結晶
を濾過し、得られた濾過ケーキを、アルコール等で洗浄
し、乾燥することにより2−(1−アルキルアミノアル
キル)−3−ヒドロキシ−1,4−ナフトキノンが得ら
れる。必要ならば 液からも生成物を回収する事ができ
る。After adding a predetermined amount of 2-hydroxy-1,4-naphthoquinone and a primary amine to a predetermined amount of a solvent to generate a primary amine salt of 2-hydroxy-1,4-naphthoquinone, Further, a predetermined amount of aldehyde was added and reacted with stirring at a predetermined temperature for 1 to 10 hours, or a predetermined amount of primary amine and aldehyde were added to a predetermined amount of solvent to generate a Schiff base. Afterwards, a predetermined amount of 2-
Hydroxy-1, tonaphthoquinone is added, and the mixture is allowed to react at a predetermined temperature for 1 to 10 hours while stirring. The precipitated crystals are filtered, and the resulting filter cake is washed with alcohol or the like and dried to obtain 2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone. If necessary, the product can also be recovered from the liquid.
本発明における2−(1−アルキルアミノアルキル)−
3−ヒドロキシ−1,4−ナフトキノン(tl)は、こ
れを熱分解することにより、2−(l−アルケニル)−
3−ヒドロキシ−1,4−ナフトキノン(F)を得るこ
とができる。ただし、次式に示すようにこの場合、化合
物(D)におけるR2は炭素数2以上のアルキル基を示
し、α位の炭素は少なくとも1つの水素を有することが
必要である。この熱分解反応は1次の反応式によって表
わされ、中間に第四級アンモニウム塩(E)を経由して
、2−(1−アルケニル)−3−ヒドロキシ−1,4−
ナフトキノン(F)が得られる。2-(1-alkylaminoalkyl)- in the present invention
By thermally decomposing 3-hydroxy-1,4-naphthoquinone (tl), 2-(l-alkenyl)-
3-hydroxy-1,4-naphthoquinone (F) can be obtained. However, as shown in the following formula, in this case, R2 in compound (D) must represent an alkyl group having 2 or more carbon atoms, and the carbon at the α position must have at least one hydrogen. This thermal decomposition reaction is expressed by the first-order reaction formula, in which 2-(1-alkenyl)-3-hydroxy-1,4-
Naphthoquinone (F) is obtained.
(D) (E) (F)ここ
で1式中RIはアルキル基又はシクロアルキル基を、R
2は上記定義と同じ意味を、RN 、アルキル、R4:
水またはアルキル、Xは酸基を表わす。(D) (E) (F) where RI in formula 1 represents an alkyl group or a cycloalkyl group;
2 has the same meaning as the above definition, RN, alkyl, R4:
Water or alkyl, X represents an acid group.
上記熱分解反応に用いられる酸としては、2−(1−ア
ルキルアミノアルキル)−3−ヒドロキシ−1,4−ナ
フトキノン(D)の7ミノ基と反応して第四級アンモニ
ウム塩を形成できる酸なら何でもよく1例えば塩酸、臭
酸、ヨウ化水素酸等の7Xロゲン化水素酸あるいは硫酸
等がある。The acid used in the above thermal decomposition reaction is an acid that can react with the 7-mino group of 2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone (D) to form a quaternary ammonium salt. For example, 7X hydrochloric acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, or sulfuric acid may be used.
上記酸の使用量は2−(1−アルキルアミノアルキル)
−3−ヒドロキシ−!、4−ナフトキノンと等モル以上
で、好ましくは1.0〜1.5モル倍を用いる。使用量
が少ないと副反応が生じ、収率が低下する。The amount of the above acid used is 2-(1-alkylaminoalkyl)
-3-Hydroxy-! , 4-naphthoquinone in an equimolar amount or more, preferably 1.0 to 1.5 times the molar amount. If the amount used is small, side reactions will occur and the yield will decrease.
また、多すぎると反応が遅くなる。In addition, if the amount is too large, the reaction will be slow.
上記反応に用いられる溶媒としては、メチルセロソルブ
、エチルセロソルブなどのグリコールエーテル、キシレ
ンなどの芳香族炭化水素、ジオキサンなどのエーテル、
酢酸ブチルなどのエステル、メチルイソブチルケトンな
どケトンが挙げられる。Solvents used in the above reaction include glycol ethers such as methyl cellosolve and ethyl cellosolve, aromatic hydrocarbons such as xylene, ethers such as dioxane,
Examples include esters such as butyl acetate, and ketones such as methyl isobutyl ketone.
反応条件は、反応温度が75℃以上、好ましくは80〜
140℃、常圧、加圧、自生圧下であり、反応時間は0
.5〜10時間程時間子分である。The reaction conditions include a reaction temperature of 75°C or higher, preferably 80°C or higher.
140℃, normal pressure, pressurization, autogenous pressure, reaction time 0
.. He is a henchman for about 5 to 10 hours.
この熱分解反応は、一般に次の様に実施される。This thermal decomposition reaction is generally carried out as follows.
所定量の2−(1−アルキルアミノアルキル)−3−ヒ
ドロキシ!、4−ナフトキノンを、所定量の溶媒中に加
え、更に室温で攪拌下に所定量の酸を加えて。A predetermined amount of 2-(1-alkylaminoalkyl)-3-hydroxy! , 4-naphthoquinone is added to a predetermined amount of solvent, and further a predetermined amount of acid is added under stirring at room temperature.
第四級アンモニウム塩を生成させた後、所定温度で0.
5〜10時間熱分解反応を行なう、この反応混合物を冷
却して析出してくる結晶を濾過し、得られた濾過ケーキ
をアルコール等で洗浄し、乾燥することにより2−(1
−アルケニル)−3−ヒドロキシ−1,4−ナフトキノ
ンの結晶が得られる。なお、必要ならば1!!掖からさ
らに生成物を回収することができる0例えば濾液を濃縮
し、冷却晶析することにより回収することができる。After generating the quaternary ammonium salt, 0.
A thermal decomposition reaction is carried out for 5 to 10 hours. The reaction mixture is cooled and the precipitated crystals are filtered. The resulting filter cake is washed with alcohol and dried to obtain 2-(1
-alkenyl)-3-hydroxy-1,4-naphthoquinone crystals are obtained. In addition, if necessary, 1! ! Further product can be recovered from the solution, for example by concentrating the filtrate and crystallizing it on cooling.
水熱分解反応は、必ずしも単離した2−(l−アルキル
アミノアルキル)−3−ヒドロキシ−1,4−ナフトキ
ノンを用いる必要はなく、2−ヒドロキシ−1,4−ナ
フトキノンとアルデヒドと第一級アミンとより得られた
、2−(l−アルキルアミノアルキル)−3−ヒドロキ
シ−1,4−ナフトキノンを含む反応混合物に酸を加え
、熱分解反応を行なうことによっても、同様に2−(1
−フルケニル)−3−?ドロキシー1.4−ナフトキノ
ンの結晶を得ることができる。In the hydrothermal decomposition reaction, it is not necessary to use isolated 2-(l-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone, and 2-hydroxy-1,4-naphthoquinone and aldehyde are combined with primary Similarly, 2-(1
-Flukenyl)-3-? Crystals of droxy 1,4-naphthoquinone can be obtained.
[実施例] 以下、実施例をあげて本発明の詳細な説明する。[Example] Hereinafter, the present invention will be explained in detail by giving examples.
実施例1
2−ヒドロキシ−1,4−ナフトキノン (ローソン)
3.50g(20,1ミリモル)をエタノール5〇−中
に加え、更にモノメチルアミン水溶液(40重tx)t
、e。Example 1 2-hydroxy-1,4-naphthoquinone (Lawson)
3.50 g (20.1 mmol) was added to 50% of ethanol, and further aqueous monomethylamine solution (40 tx) was added.
, e.
g(20,8ミリモル)を加えてアミン塩の均一溶液と
した後、ブチルアルデヒド 1.90g (28,4ミ
リモル)を加え、25℃で1.5時間反応させた。約2
0分で結晶が析出し始めた0反応終了後、析出した結晶
を濾別し、メタノールで洗浄することで目的物の粗結晶
4.43g(17,1ミリモル)を得た。収率は85.
1モル2であった。g (20.8 mmol) was added to make a homogeneous solution of the amine salt, and then 1.90 g (28.4 mmol) of butyraldehyde was added and reacted at 25° C. for 1.5 hours. Approximately 2
After completion of the reaction in which crystals began to precipitate in 0 minutes, the precipitated crystals were filtered off and washed with methanol to obtain 4.43 g (17.1 mmol) of crude crystals of the target product. Yield is 85.
It was 1 mole 2.
実施例2
実施例1のメチルアミン水溶液の代りにエチルアミン水
溶液(70重量$) 1.30g (2G、2ミIJ
モll/)を用い、反応時間を 1時間とした以外は実
施例1と同様にして、目的物の粗結晶4.43g(18
,2ミリモル)を得た。収率は80.7モル2であった
。Example 2 In place of the methylamine aqueous solution in Example 1, 1.30 g of ethylamine aqueous solution (70 wt.
The procedure was repeated in the same manner as in Example 1, except that the reaction time was 1 hour, and 4.43 g (18
, 2 mmol) was obtained. The yield was 80.7 mol2.
実施例3
実施例2のエチルアミンの代りにn−プロルアミン1.
50g(20,5ミリモル)を用いた以外は実施例2と
同様にして、目的物の粗結晶5.811g(111,[
lミリモル)を得た。収率は97.3モル2であった。Example 3 n-prolamine instead of ethylamine in Example 2 1.
5.811 g (111, [
1 mmol) was obtained. The yield was 97.3 mol2.
実施例4
2−1−メ ルアミノ−3−メ ループ ルー3−ヒド
ロキシ−14−チッ キノンd
溶媒をメタノール50mにして、ブチルアルデヒドの代
りにイソ吉草アルデヒド2.20g(25,8ミリモル
)を用いて1反応時間を3時間とした以外は実施例1と
同様にして、目的物の粗結晶3.23g(11,8ミリ
モル)を得た。収率は58.9モル2であった。Example 4 2-1-Melamino-3-meroop-3-hydroxy-14-thiquinone d The solvent was changed to 50 ml of methanol, and 2.20 g (25.8 mmol) of isovaleraldehyde was added in place of butyraldehyde. 3.23 g (11.8 mmol) of crude crystals of the target product were obtained in the same manner as in Example 1, except that the reaction time was 3 hours. The yield was 58.9 mol2.
実施例5
アルデヒドをカプリルアルデヒド3.80g(24,4
ミリモル)、アミンをシクロヘキシルアミン2.00g
(20,2ミリモル)とした以外は実施例4と同様にし
て、目的物の粗結晶8.80g(1111,5ミリモル
)を得た。収率は82.3モル2であった。Example 5 3.80 g of caprylic aldehyde (24,4
mmol), amine to cyclohexylamine 2.00g
8.80 g (1111.5 mmol) of crude crystals of the target product were obtained in the same manner as in Example 4 except that the amount was changed to (20.2 mmol). The yield was 82.3 mol2.
実施例6
0−ンン8.0Gg(34,5ミリモル)、i−プロピ
ルアミン2.06g(34,5ミリモル)をメタノール
10〇−中に加え、更に水浴下(27℃)、これにn
−ドデシルアルデヒド7.82g (41,3ミリモ
ル)を加え、 3時間反応させた0反応終了後、析出し
た結晶を濾別し、メタノールで洗浄し、2−(+−i−
プロピルアミン)−3−ヒドロキシ−1,4−ナフトキ
ノン9.78gを得た。収率は70モル2であった。Example 6 8.0 Gg (34.5 mmol) of 0-propylamine and 2.06 g (34.5 mmol) of i-propylamine were added to 100 g (34.5 mmol) of i-propylamine, and further added to this in a water bath (27°C).
7.82 g (41.3 mmol) of -dodecylaldehyde was added and reacted for 3 hours. After the reaction, the precipitated crystals were filtered off, washed with methanol, and 2-(+-i-
9.78 g of (propylamine)-3-hydroxy-1,4-naphthoquinone was obtained. The yield was 70 mol2.
また、濾液をHPLに (高性能液体クロマトグラフィ
ー)で分析した結果、未反応ローソン0.21g、目的
物2.72g i:濾液中に確認した。この濾液中の目
的物を加算すると、収量は12.48g(31,2ミリ
モル)であり、収率は80.4モル2となる。Further, as a result of analyzing the filtrate by HPL (high performance liquid chromatography), 0.21 g of unreacted lawson and 2.72 g of the target substance were confirmed in the filtrate. When the target product in this filtrate is added, the yield is 12.48 g (31.2 mmol), and the yield is 80.4 mol2.
実施例7
1−プロピルアミンの代わりにn−ブチルアミン2.5
5g(34,5ミリモル)を用いた以外は実施例6と同
様にして2−(1−n−ブチル7ミノ)−3−ヒドロキ
シ−1,4−ナフトキノン8.72g(47モル2)を
得た。また濾液をHPLCで分析した結果、未反応ロー
ソン0.11g、目的物8.57gを確認した。総収量
は13.29g(32,1ミリモル)、収率は83.0
モル2であった。Example 7 2.5 n-butylamine instead of 1-propylamine
8.72 g (47 moles) of 2-(1-n-butyl7mino)-3-hydroxy-1,4-naphthoquinone was obtained in the same manner as in Example 6, except that 5 g (34.5 mmol) was used. Ta. Further, as a result of HPLC analysis of the filtrate, 0.11 g of unreacted lawson and 8.57 g of the target product were confirmed. Total yield: 13.29 g (32.1 mmol), yield: 83.0
It was mol 2.
実施例8
アミンとしてt−ブチルアミン2.55g(34,5ミ
リモル)を用いて以外は実施例6と同様にして、2−(
l−t−ブチルアミノドデシル)−3−ヒドロキシ−1
,4−ナフドキノン5.8?、を得た。また濾液をHP
LCで分析したところ、未反応ローンン242g、目的
物1.49gを確認した。収量7.16g(17,3ミ
リモル)、収率50.1モル2であった。Example 8 2-(
l-t-butylaminododecyl)-3-hydroxy-1
, 4-nafdoquinone 5.8? , obtained. Also, the filtrate is
When analyzed by LC, 242 g of unreacted raw material and 1.49 g of the target product were confirmed. The yield was 7.16 g (17.3 mmol), and the yield was 50.1 mol2.
実施例9
o −ソy19.7g(113ミjj %A/) 、
40$ )チk 7ミン水溶液8.77g(目3ミリモ
ル)、メタノール300−1水20゜3gを室温にて攪
拌し、これにn−ドデシルアルデヒド25.0g (1
35,8ミリモル)を加え3時間反応させた。析出した
結晶を濾別し、メタノールで洗浄し2−(1−メチルア
ミノドデシル)−3−ヒドロキシ−1,4−ナフトキノ
ンの粗結晶33.Illg(91,4ミリモル) (8
0,13モル2)を得た。又、濾液をHPLCで分析し
たところ、目的物3.28g(8,84ミリモル)及び
未反応ローソン1.45g(8,33ミリモル)を確認
した。Example 9 o-Soy 19.7g (113mijj%A/),
40$) Thik 7mine aqueous solution 8.77g (3 mmol) and methanol 300-1 water 20°3g were stirred at room temperature, and to this was added 25.0g n-dodecylaldehyde (1
35.8 mmol) was added and reacted for 3 hours. The precipitated crystals were filtered and washed with methanol to obtain crude crystals of 2-(1-methylaminododecyl)-3-hydroxy-1,4-naphthoquinone 33. Illg (91.4 mmol) (8
0.13 mol 2) was obtained. Further, when the filtrate was analyzed by HPLC, 3.28 g (8.84 mmol) of the target product and 1.45 g (8.33 mmol) of unreacted lawson were confirmed.
実施例10
溶媒をエタノールの代わりにTHFとし、ブチルアルデ
ヒドの代わりにn−ドデシルアルデヒド4.44g(2
4,1ミリモル)を用いた以外は実施例1と同様に反応
を行ない、得られた均一溶液の一部を取りHPLCで分
析したところ、 2−(1−メチル7ミノドデシル)−
3−ヒドロキシ−1,4−ナフトキノン25.3厘g(
0,15ミリモル)を確認した。収率は89.0モル2
であった。Example 10 The solvent was THF instead of ethanol, and 4.44 g (2
The reaction was carried out in the same manner as in Example 1, except that 4.1 mmol) was used, and a portion of the resulting homogeneous solution was analyzed by HPLC.
3-hydroxy-1,4-naphthoquinone 25.3 g (
0.15 mmol). The yield is 89.0 mol2
Met.
以上の結果得られた化合物のIR((ニー0の伸縮振動
数υ、cm’ ) 、 NMR、融点(m、p、)を第
1表に、元素分析結果を第2表に示す。The IR ((knee 0 stretching frequency υ, cm'), NMR, and melting point (m, p,) of the compound obtained above are shown in Table 1, and the elemental analysis results are shown in Table 2.
実施例11
実施例7で得られた2−(1−n−プチルアミノドデ第
1表
第2表
シル)−3−ヒドロキシ−1,4−ナフトキノン(h)
3.34g(8,09ミリモル)を、メチルセロソル
ブ3〇−中に加え、更に硫酸0.+12g(8J2ミリ
モル)を攪拌下に室温で加えて、硫酸塩の均一溶液とし
た後、120℃に加熱してで1時間熱分解反応を行なっ
た0反応終了後、得られる反応液を冷却して析出した結
晶を濾別し、メタノールでよく洗浄することにより、2
−(1−ドデセニル)−3−ヒドロキシ−1,4−ナフ
トキノンの結晶2.23g(6,58ミリモル) (8
1,1モル2)を得た。また、濾液をHPL(:で分析
したところ、0.11g (7)生成物(0,32ミ!
J モル)(4,0モルlDを確認した。Example 11 2-(1-n-butylaminodode Table 1 Table 2)-3-hydroxy-1,4-naphthoquinone (h) obtained in Example 7
3.34 g (8.09 mmol) was added to methyl cellosolve 30- and then 0.0 g of sulfuric acid was added. +12 g (2 mmol of 8J) was added at room temperature with stirring to make a homogeneous solution of sulfate, and then heated to 120°C and subjected to a thermal decomposition reaction for 1 hour. After the reaction was completed, the resulting reaction solution was cooled. By filtering the precipitated crystals and washing thoroughly with methanol, 2.
-(1-dodecenyl)-3-hydroxy-1,4-naphthoquinone crystals 2.23 g (6,58 mmol) (8
1.1 mol 2) was obtained. In addition, when the filtrate was analyzed by HPL (:), 0.11 g (7) of the product (0.32 mm!
J mol) (4,0 mol ID was confirmed.
実施例12
実施例8で得られた2−(1−t−ブチルアミモー ド
デシル)−3−ヒドロキシ−1,4−ナフトキノン(i
)3.32g(8,04ミリモル)を(h)の代わりに
用いた以外は、実施例11と同様にして2−(l−ドデ
セニル)−3−ヒドロキシ−1,4−ナフトキノンの結
晶2.54g (7,47ミリモル)(92,13モル
2)を得た。又、濾液をHPLCで分析したところ、1
45膳g(0,43ミリモル)(5,3モル2)を確認
した。Example 12 2-(1-t-butylamimodedodecyl)-3-hydroxy-1,4-naphthoquinone (i
Crystals of 2-(l-dodecenyl)-3-hydroxy-1,4-naphthoquinone were prepared in the same manner as in Example 11, except that 3.32 g (8.04 mmol) of 2. 54 g (7.47 mmol) (92.13 mol 2) were obtained. In addition, when the filtrate was analyzed by HPLC, 1
45 g (0.43 mmol) (5.3 mol2) was confirmed.
実施例13
実施例3で得られた2−(1−n−ブチルアミノブチル
)−3−ヒドロキシ−1,4−ナフトキノン(c) 3
.0Og(9,97ミリモル)をメチルセロソルブ5o
−中に加え、室温で攪拌下に濃塩酸1.15g(11,
0ミリモル)を加えて塩酸塩を生成させた後、この反応
液を120℃に加熱して 1時間保ち、熱分解反応を行
なった0反応終了後、反応生成液を減圧下で濃縮し、得
られたオイルをシリカゲルカラム(酢酸エチル:n−へ
キサン=l二〇で分離精製し、 2−(1−ブチニル)
−3−ヒドロキシ−1,4−ナフトキノンの結晶1.8
5g(8,11ミリモル)(81,4モル2)を得た。Example 13 2-(1-n-butylaminobutyl)-3-hydroxy-1,4-naphthoquinone (c) 3 obtained in Example 3
.. 00g (9.97 mmol) of methyl cellosolve 5o
- 1.15 g of concentrated hydrochloric acid (11,
After the reaction solution was heated to 120°C and kept for 1 hour to carry out a thermal decomposition reaction, the reaction product solution was concentrated under reduced pressure and the obtained The resulting oil was separated and purified using a silica gel column (ethyl acetate: n-hexane = 20), and purified with 2-(1-butynyl).
-3-hydroxy-1,4-naphthoquinone crystals 1.8
5 g (8.11 mmol) (81.4 mol 2) were obtained.
実施例14
実施例11において、2−(l−ブチルアミノブチル)
−3−ヒドロキシ−1,4−ナフトキノンの代りに実施
例4で得られた2−(l−メチルアミノ−3−メチル−
ブチル)−3−ヒドロキシ−1,4−ナフトキノン(d
) 2.00g(7,33ミリモル)を用い、塩酸の量
を0.80g(7,87ミリモル)とした以外は実施例
11と同様にして、 2−(3−メチル−ブテニル)−
3−ヒドロキシ−1,4−ナフトキノンの結晶1.30
g(5,37ミリモル)(73,3モル駕)を得た。Example 14 In Example 11, 2-(l-butylaminobutyl)
-3-hydroxy-1,4-naphthoquinone was replaced with 2-(l-methylamino-3-methyl-
butyl)-3-hydroxy-1,4-naphthoquinone (d
) 2-(3-methyl-butenyl)-
Crystals of 3-hydroxy-1,4-naphthoquinone 1.30
g (5.37 mmol) (73.3 mol) was obtained.
実施例15
30−ガラスオートクレーブに2−(1−メチルアミノ
ドデシル)−3−ヒドロキシ−1,4−ナフトキノンを
1.0Og(2,87ミリモル)、濃硫酸305.8m
g (原料に対して1.1 ミリモル倍)及びキシレ
ン20−を入れ、攪拌しながら120℃に加熱し、その
温度で1時間保った。放冷後、ベンゼン−水系で抽出し
、有機層を硫酸ナトリウムで乾燥後、溶媒を留去した後
、メタノールにより再結品行なった。これにより2−(
l−ドデセニル)−3−ヒドロキシ−1,4−ナフトキ
ノン734.8層8を得た。また、再結晶濾液をHPL
Cにより分析した結果、濾液中に2−ヒドロキシ−1,
4−ナフトキノン!2.4■g、原料0.7履g、目的
物15.5−gを確認した。収率等を第3表に示す。Example 15 In a 30-glass autoclave, 1.0 Og (2.87 mmol) of 2-(1-methylaminododecyl)-3-hydroxy-1,4-naphthoquinone and 305.8 m of concentrated sulfuric acid were added.
g (1.1 mmol times the raw material) and 20 mm of xylene were added, heated to 120° C. with stirring, and kept at that temperature for 1 hour. After cooling, the mixture was extracted with a benzene-water system, the organic layer was dried over sodium sulfate, the solvent was distilled off, and the mixture was reconstituted with methanol. This results in 2-(
1-Dodecenyl)-3-hydroxy-1,4-naphthoquinone 734.8 Layer 8 was obtained. In addition, the recrystallization filtrate was subjected to HPL.
As a result of analysis by C, 2-hydroxy-1,
4-Naphthoquinone! 2.4 g, raw material 0.7 g, and target material 15.5 g were confirmed. The yield etc. are shown in Table 3.
実施例16〜18
溶媒を第3表に示す溶媒に代えて、実施例13と同様に
行なった。但し抽出は酢酸エチル−水系で行なった。得
られた収率は第3表に示す。Examples 16 to 18 The same procedure as in Example 13 was carried out except that the solvent was replaced with the solvent shown in Table 3. However, extraction was performed using an ethyl acetate-water system. The yields obtained are shown in Table 3.
実施例19
酢酸ブチル7(1+ae中で2−ヒドロキシ−1,4−
ナフトキノン3.52g(20,2ミリモル)、メチル
アミン(4oz水溶液1.80g) (20,8ミリモ
ル)及びn−ドデシルアルデヒド4.40g(23,1
1ミリモル)を室温で2時間反応させた。Example 19 Butyl acetate 7 (2-hydroxy-1,4- in 1+ae)
3.52 g (20.2 mmol) naphthoquinone, methylamine (1.80 g 4 oz aqueous solution) (20.8 mmol) and 4.40 g (23.1 mmol) n-dodecylaldehyde.
1 mmol) was reacted at room temperature for 2 hours.
得られた反応液をHPLCで分析したところ7.28g
(19J ミリモル)の2−(1−メチルアミノドデシ
ル)−3−ヒドロキシ−1,4−ナフトキノンを含むこ
とが確認された1反応混合液に濃硫酸2.08g(20
,2ミリモル)を徐々に加えて硫酸塩の溶液とした後(
50℃で均一溶液となる)、還流下で1時間熱分解反応
を行なった。When the obtained reaction solution was analyzed by HPLC, it was 7.28g.
(19 J mmol) of 2-(1-methylaminododecyl)-3-hydroxy-1,4-naphthoquinone was mixed with 2.08 g (20 J mmol) of concentrated sulfuric acid.
, 2 mmol) was gradually added to form a solution of sulfate (
A homogeneous solution was formed at 50° C.), and the thermal decomposition reaction was carried out under reflux for 1 hour.
反応終了後1反応液を冷却し、析出した結晶を濾別し、
メタノールで洗浄することにより2−(1−ドデセニル
)−3−ヒドロキシ−1,4−ナフトキノンの結晶5.
13g(15,1ミ!J % JLz)(74,8−!
1L4)を得り、マた、吐液中にHPL(:分析により
0.70g(2,013ミリモル)(10,2モル2)
の生成物を確認した。After the completion of the reaction, the reaction solution was cooled, and the precipitated crystals were filtered out.
5. Crystals of 2-(1-dodecenyl)-3-hydroxy-1,4-naphthoquinone are obtained by washing with methanol.
13g (15,1 mi! J % JLz) (74,8-!
1L4) was obtained, and HPL (: 0.70 g (2,013 mmol) (10.2 mol2) was obtained in the ejected liquid by analysis.
The product was confirmed.
これより、この反応では2−ヒドロキシ−1,4−ナフ
トキノンより2−(1−ドデセニル)−3−ヒドロキシ
−1,4−ナフトキノンを85.Hの収率で合成したこ
とになる。Therefore, in this reaction, 2-(1-dodecenyl)-3-hydroxy-1,4-naphthoquinone is produced by 85. This means that it was synthesized with a high yield of H.
比較例1
2−ヒドロキシ−1,4−ナフトキノン2.5g(14
,4ミリモル)を酢酸501中に加え、さらにドデシル
アルデヒド5.4g(2−ヒドロキシ−1,4−ナフト
キノンに対して2.03モル倍)及び濃塩酸7.5g
(2−ヒドロキシ−1,4−ナフトキノンに対して1.
4モル倍)を触媒どして添加し、85℃で2時間反応さ
せた。得られた反応液を約5℃に冷却したが、結晶が析
出しないので、水3001中に入れた後、ベンゼン20
0w+jで抽出した。この有機層を炭酸ナトリウム1z
水溶液150−で2回、ざらに水150dで洗浄した後
、無水芒硝で乾燥し、ベンゼンを留去して得られた油層
をシリカゲルカラムで分離精製することにより、2−(
l−ドデセニル)−3−ヒドロキシ−1,4−ナフトキ
ノン!、97gを得た。収率は40.2モル2であった
。Comparative Example 1 2.5 g of 2-hydroxy-1,4-naphthoquinone (14
, 4 mmol) in acetic acid 501, and further added 5.4 g of dodecylaldehyde (2.03 times the mole of 2-hydroxy-1,4-naphthoquinone) and 7.5 g of concentrated hydrochloric acid.
(1 for 2-hydroxy-1,4-naphthoquinone.
4 mole times) was added as a catalyst, and the mixture was reacted at 85°C for 2 hours. The resulting reaction solution was cooled to about 5°C, but since no crystals precipitated, it was poured into 3001 ml of water and then 20 ml of benzene.
Extracted at 0w+j. Add this organic layer to 1z of sodium carbonate.
After washing twice with 150 d of aqueous solution and 150 d of water, drying with anhydrous sodium sulfate and distilling off benzene, the resulting oil layer was separated and purified using a silica gel column.
l-dodecenyl)-3-hydroxy-1,4-naphthoquinone! , 97g was obtained. The yield was 40.2 mol2.
[発明の効果]
本発明で得られた2−(1−アルキルアミノアルキル)
−3−ヒドロキシ−!、4−ナフトキノンは、その物日
体、生理活性を有すると思われるが、更にこの物の脱ア
ミノ化反応によって、有用な医薬、農薬中間体である2
−(l−アルケニル)−3−ヒドロキシ−1、トナフト
キノンおよび2−フルキル−3−ヒドロキシ−1,4−
ナフトキノンに導く事ができる。[Effect of the invention] 2-(1-alkylaminoalkyl) obtained by the present invention
-3-Hydroxy-! , 4-naphthoquinone is thought to have physiological activity in its own right, but it can also be used as a useful pharmaceutical and agricultural intermediate by deamination reaction.
-(l-alkenyl)-3-hydroxy-1, tonaphthoquinone and 2-furkyl-3-hydroxy-1,4-
It can lead to naphthoquinone.
手続ネ甫正書 (自発) 工6 昭和63年3月腫日Procedure Nefusho (self-motivated) Engineering 6 March 1985 Tumor Day
Claims (5)
R^2は炭素数2以上のアルキル基を示す。) で表される新規な2−(1−アルキルアミノアルキル)
−3−ヒドロキシ−1,4−ナフトキノン。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is an alkyl group or a cycloalkyl group,
R^2 represents an alkyl group having 2 or more carbon atoms. ) Novel 2-(1-alkylaminoalkyl) represented by
-3-hydroxy-1,4-naphthoquinone.
3以上の脂肪族アルデヒドとを第一級アミンの存在下に
不活性有機溶媒中で反応させることを特徴とする2−(
1−アルキルアミノアルキル)−3−ヒドロキシ−1,
4−ナフトキノンの製造方法。(2) A 2-(
1-alkylaminoalkyl)-3-hydroxy-1,
Method for producing 4-naphthoquinone.
−(1−アルキルアミノアルキル)−3−ヒドロキシ−
1,4−ナフトキノンの製造方法。(3) 2 according to claim 2, wherein the reaction temperature is 35°C or lower.
-(1-alkylaminoalkyl)-3-hydroxy-
Method for producing 1,4-naphthoquinone.
R^2は炭素数2以上のアルキル基を示し、α位の炭素
に少なくとも1つの水素を有す。) で表される新規な2−(1−アルキルアミノアルキル)
−3−ヒドロキシ−1,4−ナフトキノンを不活性溶媒
中、酸の存在下に熱分解させることを特徴とする2−(
1−アルケニル)−3−ヒドロキシ−1,4−ナフトキ
ノンの製造方法。(4) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is an alkyl group or a cycloalkyl group,
R^2 represents an alkyl group having 2 or more carbon atoms, and has at least one hydrogen at the α-position carbon. ) Novel 2-(1-alkylaminoalkyl) represented by
2-( characterized by thermally decomposing -3-hydroxy-1,4-naphthoquinone in an inert solvent in the presence of an acid.
A method for producing 1-alkenyl)-3-hydroxy-1,4-naphthoquinone.
に記載の2−(1−アルケニル)−3−ヒドロキシ−1
,4−ナフトキノンの製造方法。(5) Claim 4, wherein the acid is sulfuric acid or hydrohalic acid.
2-(1-alkenyl)-3-hydroxy-1 as described in
, 4-naphthoquinone manufacturing method.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4175588A JP2592421B2 (en) | 1988-02-23 | 1988-02-23 | Novel 2- (1-alkylaminoalkyl) -3-hydroxy-1,4-naphthoquinone and method for producing the same, and method for producing 2- (1-alkenyl) -3-hydroxy-1,4-naphthoquinone using the compound |
US07/310,623 US4980489A (en) | 1988-02-23 | 1989-02-15 | 2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone |
DE89103105T DE68906563T2 (en) | 1988-02-23 | 1989-02-22 | 2 (1-alkylaminoalkyl) -3-hydroxy-1,4-naphthoquinone Process for the preparation and process for the preparation of 2- (1-alkenyl) -3-hydroxy-1,4-naphthoquinone and 2-alkyl-3- acyloxy-1,4 naphthoquinone. |
EP89103105A EP0330186B1 (en) | 1988-02-23 | 1989-02-22 | 2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone, process for its production and processes for producing 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinone and 2-alkyl-3-acyloxy-1,4-naphthoquinone by using it |
KR1019890002108A KR950004043B1 (en) | 1988-02-23 | 1989-02-22 | 2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinoue, process for its production and process for producing 2-(1-alkenyl)-3-2-alkyl-3-acylaxy-1,4-naphthoquinone by using it |
BR898900794A BR8900794A (en) | 1988-02-23 | 1989-02-22 | 2- (1-ALKYLAMINOALKYL) -3-HYDROXY-1,4-NAFTOQUINONE, PROCESS FOR ITS PRODUCTION, AND PROCESSES FOR THE PRODUCTION OF 2- (1-ALKENYL) -3-HYDROXY-1,4-NAPHTOQUINONE AND 2- ALKYL-3-ACYLOXY-1,4-NAPHTOQUINONE THROUGH ITS USE |
US07/835,024 US5225578A (en) | 1988-02-23 | 1992-02-18 | 2-(1-alkylaminoalkyl)-3-hydroxy-1,4-naphthoquinone, process for its production and processes for producing 2-(1-alkenyl)-3-hydroxy-1,4-naphthoquinone and 2-alkyl-3-acyloxy-1,4-naphthoquinone by using it |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4175588A JP2592421B2 (en) | 1988-02-23 | 1988-02-23 | Novel 2- (1-alkylaminoalkyl) -3-hydroxy-1,4-naphthoquinone and method for producing the same, and method for producing 2- (1-alkenyl) -3-hydroxy-1,4-naphthoquinone using the compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01216952A true JPH01216952A (en) | 1989-08-30 |
JP2592421B2 JP2592421B2 (en) | 1997-03-19 |
Family
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Application Number | Title | Priority Date | Filing Date |
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JP4175588A Expired - Fee Related JP2592421B2 (en) | 1988-02-23 | 1988-02-23 | Novel 2- (1-alkylaminoalkyl) -3-hydroxy-1,4-naphthoquinone and method for producing the same, and method for producing 2- (1-alkenyl) -3-hydroxy-1,4-naphthoquinone using the compound |
Country Status (1)
Country | Link |
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JP (1) | JP2592421B2 (en) |
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1988
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JP2592421B2 (en) | 1997-03-19 |
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