JPS636540B2 - - Google Patents
Info
- Publication number
- JPS636540B2 JPS636540B2 JP54096665A JP9666579A JPS636540B2 JP S636540 B2 JPS636540 B2 JP S636540B2 JP 54096665 A JP54096665 A JP 54096665A JP 9666579 A JP9666579 A JP 9666579A JP S636540 B2 JPS636540 B2 JP S636540B2
- Authority
- JP
- Japan
- Prior art keywords
- compound according
- basic compound
- reaction
- lithium
- structural formula
- 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.)
- Expired
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 27
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 20
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 17
- -1 alkali metal amide Chemical class 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000007514 bases Chemical class 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 150000002431 hydrogen Chemical group 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical class ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã
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ããã³ãã®è£œé æ³ã«é¢ãããDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel compound having a substituted amino group and a method for producing the same.
ãšããã·æš¹èçã®ç¡¬åå€ãšããŠã¯ã倧å¥ããŠè
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ãã€ãŠãããããã®ãã¡ãããçšããããŠããã
ã®ãäžã€ã«ããªã¢ãã³ãããã Hardening agents for epoxy resins and the like can be broadly classified into amines such as aliphatic polyamines and aromatic polyamines, acid anhydrides including phthalic anhydride, polyamide resins, polysulfide resins, and the like. The physical properties of the resin vary depending on the type of curing agent used, and one of the most commonly used curing agents is polyamine.
ãã®ãããªèæ¯ã«ç«ã¡ãæ¬çºæè
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æ§é åŒïŒïŒã§ç€ºãããå¡©åºæ§ååç©ã以äžã
ãååç©ïŒïŒããšç¥ãããèŠãåºãã«è³ã€ãã Against this background, the present inventors developed a basic compound represented by the following structural formula () [hereinafter referred to as
``Compound ()''] was discovered.
ïŒåŒäžãã¯æ°ŽçŽ ãççŽ æ°ïŒããïŒã®ã¢ã«ãã«
åºãããã²ã³ãŸãã¯ãããåºãïœããã³ïœã¯ïŒã
ãïŒã®æŽæ°ãè¡šãããïŒ
ããªãã¡ãæ¬çºæã¯ãæ§é åŒïŒïŒ
ïŒåŒäžããïœããã³ïœã¯åèšãšåãæå³ãè¡šã
ããïŒã§ç€ºãããæ°èŠãªå¡©åºæ§ååç©ã§ããã (In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4.) This is a novel basic compound represented by the formula (wherein, X, m and n have the same meanings as above).
ååç©ïŒïŒã«ãããŠïœããã³ïœã®å¥œãŸããæ
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æ§ã®äŸã¯ãæ°ŽçŽ ãã¡ãã«åºã
ãšãã«åºãŸãã¯ã¯ãã«åºã§ããã A preferred embodiment of m and n in compound () is that (m+n) is an integer from 2 to 5.
Preferred embodiments of X include hydrogen, methyl group,
It is an ethyl group or a chloro group.
ãŸãæ¬çºæã¯ãäžèšã®æ§é åŒïŒïŒã§ç€ºããã
ã¢ãã³ããããã«å¯Ÿå¿ããæ§é åŒïŒïŒã§ç€ºãã
ãã¢ã«ã«ãªéå±ã¢ããã®å
±åäžã«ãã¹ãã¬ã³çœ®æ
äœïŒïŒãšåå¿ãããããšãç¹åŸŽãšããäžèšã®æ§
é åŒïŒïŒã§ç€ºãããæ°èŠãªå¡©åºæ§ååç©ã®è£œé
æ³ã§ããã Further, the present invention is characterized in that an amine represented by the following structural formula () is reacted with a styrene substituted product () in the coexistence of an alkali metal amide represented by the corresponding structural formula (). This is a method for producing a novel basic compound represented by the structural formula ().
ïŒåŒäžãã¯æ°ŽçŽ ãççŽ æ°ïŒããïŒã®ã¢ã«ãã«
åºãããã²ã³ãŸãã¯ãããåºãïœããã³ïœã¯ïŒã
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ã¢ã«ã«ãªéå±ã¢ããïŒïŒã«å¯Ÿãã奜ãŸããæ
æ§ã®äžã€ã¯ãªããŠã ã¢ããã§ããã (In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4.) One of the preferred embodiments for the alkali metal amide () is lithium amide. be.
æ§é åŒïŒïŒã§ç€ºãããã¢ãã³ããªããŠã ã¢ã
ããžãšåå¿ãããããã®å¥œãŸããè©Šè¬ã®äžã€ã¯ã¢
ã«ãã«ãªããŠã ã§ãããã¢ã«ãã«ãªããŠã ãšããŠ
奜ãŸããè©Šè¬ã®äžã€ã¯ãã«ãã«âããã«ãªããŠã
ã§ããã One of the preferred reagents for reacting the amine represented by the structural formula () to lithium amide is an alkyl lithium, and one of the preferred reagents as the alkyl lithium is n-butyl lithium.
æ¬åå¿ã¯äžæŽ»æ§ææ©æ¶²äœã®å
±åäžã«åå¿ãè¡ãª
ãããšãã§ãããäžæŽ»æ§ææ©æ¶²äœãšããŠããããµ
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ãã«ããã³ãŒã³ããã«ãšã³ã®ããããããŸãã¯ïŒ
皮以äžã®æ¶²äœã®æ··åç©ãçšããããšãæãŸããã This reaction can also be carried out in the presence of an inert organic liquid. As an inert organic liquid, hexane, cyclohexane, tetrahydrofuran, ether, benzene, toluene, or 2
It is desirable to use a mixture of more than one species of liquid.
åå¿ã®ææ³ãšããŠã¯ãæ§é åŒïŒïŒã§ç€ºããã
ã¢ãã³ãšã¢ã«ãã«ãªããŠã ã®æ··åç©ã«ã¹ãã¬ã³çœ®
æäœãå ããæ¹æ³ã奜ãŸããææ³ã®äžã€ã§ããã One of the preferred reaction methods is to add a styrene substitute to a mixture of an amine represented by the structural formula () and an alkyl lithium.
以äžã«ååç©ïŒïŒã補é ããäžè¬çãªæ¹æ³ã®
äŸã瀺ãã Examples of general methods for producing compound () are shown below.
æ¬åå¿ã¯ãäžèšã®æ§é åŒïŒïŒã§ç€ºãããã¢ã
ã³ã以äžãã¢ãã³ïŒïŒããŸãã¯åã«ãã¢ãã³ã
ãšç¥ç§°ãããããããã«å¯Ÿå¿ããã¢ã«ã«ãªéå±ã¢
ããïŒïŒã®å
±åäžã«ãã¹ãã¬ã³çœ®æäœïŒïŒãš
åå¿ããããã®ã§ããã This reaction is performed using an amine represented by the following structural formula () [hereinafter referred to as "amine ()" or simply "amine"]
] is reacted with a styrene substituted product () in the coexistence of the corresponding alkali metal amide ().
ã¢ã«ã«ãªéå±ãšããŠã¯ããªããŠã ãåå¿æ§ã®é«
ããåå¿æäœã®å®¹æãçãã奜ãŸããããªããŠã
ã¢ããã®å¥œãŸãã調補æ³ã¯ãã¢ãã³ãšã¢ã«ãã«ãª
ããŠã ãããšãã«ãªããŠã ãæ°ŽçŽ åã¢ã«ãããŠã
ãªããŠã ãæ°ŽçŽ åãªããŠã çãåå¿ãããæ¹æ³ã§
ãããããã®äžã§ãã溶åªãžã®æº¶è§£åºŠãæäœæ§ç
ããã¢ã«ãã«ãªããŠã ã䜿çšããããšãç¹ã«å¥œãŸ
ãããååç©ïŒïŒã«çžåœãããªããŠã ã¢ãã
ãã以äžåã«ããªããŠã ã¢ããããšåŒç§°ããã As the alkali metal, lithium is preferred due to its high reactivity and ease of reaction operation. A preferred method for preparing lithium amide is to react an amine with alkyl lithium, phenyl lithium, aluminum lithium hydride, lithium hydride, etc. Among these, alkyl lithium is used because of its solubility in solvents, operability, etc. It is particularly preferable to do so. The lithium amide corresponding to the compound () will be simply referred to as "lithium amide" hereinafter.
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ãã Examples of styrene substitutes include styrene, alkylstyrenes such as methylstyrene and ethylstyrene, halogenated styrenes including chlorostyrene and bromostyrene, and nitrated styrenes. Among these, one example of a more preferred embodiment is styrene and chlorostyrene.
ã¢ãã³ã®å¥œãŸããäŸãšããŠã¯ãïŒïœïŒïœïŒãïŒ
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ïŒïœïŒãïŒãïŒããã³ïŒã®ã¢ãã³ã§ããã As a preferable example of the amine, (m+n) is 2
Starting with diethylenetriamine, (m
+n) are 3, 4 and 5 amines.
æ¬åå¿ã«ãããŠã¯ããªããŠã ã¢ããïŒïŒã¯è§Š
åªçäœçšãè¡ãªãããã®ããšã¯ãæ¬åå¿ã®å€§ããª
ç¹åŸŽã®äžã€ã§ãããããªãã¡ããªããŠã ã¢ãã
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çšã§ååã§ããã奜ãŸããã¯ã¢ã«æ¯ã§0.001åãª
ãã0.5åéãããã«å¥œãŸããã¯0.01åãªãã0.2
åéã§ããããã®éããªããŠã ã¢ããïŒïŒã®æ¿
床ãåå¿é床ãæ¯é
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ããã In this reaction, lithium amide () acts as a catalyst. This is one of the major features of this reaction. That is, it is sufficient to use lithium amide () in an amount equal to or less than the molar amount of the styrene substituted product, preferably 0.001 to 0.5 times the molar ratio, and more preferably 0.01 to 0.2 times the molar ratio.
It's double the amount. At this time, it should be kept in mind that the concentration of lithium amide () controls the reaction rate.
ãªããŠã ã¢ããïŒïŒã¯åå¿ç³»ã«å
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žçã®æŽ»æ§æ°ŽçŽ ãæããç©è³ªãšåå¿
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ã¯ããªããŠã ã¢ããïŒïŒãææé以äžäœ¿çšãã
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ãªããŠã ãšããŠã¯ãã¡ãã«ãªããŠã ããšãã«ãªã
ãŠã ãããã«ãªããŠã çãçšããããšãã§ãã
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ãã Lithium amide () contains water coexisting in the reaction system,
Since it is deactivated by reacting with substances containing active hydrogen such as alcohols and acids, it is preferable that the raw materials and solvents used be purified by dehydration in advance, but if it is unavoidable,
When these active hydrogen-containing substances are mixed, it is desirable to use more than the intended amount of lithium amide. As already mentioned, lithium amides can be easily prepared, for example, by reacting an alkyllithium with an amine. As the alkyl lithium, methyl lithium, ethyl lithium, butyl lithium, etc. can be used, but among these, n-butyl lithium, which is also produced industrially, is particularly preferred from the viewpoint of easy availability.
ã¢ãã³ïŒïŒã®ã¹ãã¬ã³çœ®æäœã«å¯Ÿãã䜿çšé
ã¯ãã¢ã«æ¯ã§0.5åãªããïŒåéã奜ãŸãããã
ãã«å¥œãŸããã¯0.8åãªããïŒåéã§ãããã¢ã
ã³ïŒïŒã®éãéå°ã§ãããšãçæç©ïŒïŒã®å
éãæžå°ãããšåæã«ãã¢ãã³ã«ïŒåïŒïœïŒïœïŒ
ã®å Žåã¯äžèšæ§é åŒïŒïŒã§ç€ºãããïŒãªãã
ïŒå以äžã®ã¹ãã¬ã³çœ®æäœãä»å ããå¯çæç©ã
çæããå¯èœæ§ãããã®ã§å¥œãŸãããªãã The amount of amine () to be used relative to the styrene substituted product is preferably 0.5 to 5 times, more preferably 0.8 to 2 times, in terms of molar ratio. If the amount of amine () is too small, the yield of product () will decrease and at the same time the amine will contain two (m=n=
In the case of I, it is not preferable because there is a possibility that by-products having three or more styrene substituents (represented by the following structural formula ()) or to which three or more styrene substituents are added may be produced.
ãªããŠã ã¢ããïŒïŒãšã¢ãã³ïŒïŒã®æ··å液
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ãã There are, for example, the following two methods for reacting the mixture of lithium amide () and amine () with the styrene substitute. The first method is to add a mixture of the former to the styrene substituted product. The second method is to add a styrene substitute to a mixture of lithium amide and amine.
第ïŒã®æ¹æ³ã¯ãå¯çæç©ïŒïŒã®çæãå€ããª
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èŠã¯åå¿å®¹åšãïŒåšã§ããããšããªããŠ
ã ã¢ãã液ã®ç§»ãããã®æäœãäžèŠã§ããããšãª
ã©ã®é·æãããããã第ïŒã®æ¹æ³ãããæšå¥šãã
ãã The first method has the disadvantage of increasing the production of by-products (), whereas the second method requires only one reaction vessel and the need to transfer the lithium amide solution. The second method is more recommended because it has advantages such as not requiring any additional operations.
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èèªæçåæ°ŽçŽ ããã³ãŒã³ããã«ãšã³ããã·ã¬ã³
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ãããã The reaction in the present invention can also be carried out in the presence of an inert solvent. Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as diethyl ether, dibutyl ether, dioxane, and tetrahydrofuran, dimethyl sulfoxide, Nã»N-
Liquids that do not react with lithium amide under the reaction conditions can be used, such as aprotic polar solvents such as dimethylformamide and hexamethylphosphoric triamide. Among these, hexane, cyclohexane, benzene, tetrahydrofuran, ether, toluene and the like are more preferred. Aliphatic hydrocarbons such as hexane are commonly used as completely inert solvents.
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0.1åãªãã50åã奜ãŸããããã奜ãŸããã¯0.5
åãªãã20åã§ããã The amount of solvent used is the volume of the styrene substituted product.
Preferably 0.1 to 50 times, more preferably 0.5
It is 20 to 20 times larger.
æ¬çºæã®åå¿ãè¡ãªã枩床ã«ã€ããŠã¯ç¹ã«å¶é
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èŠã§ããããŸãåå¿æ··åç©ã¯æ¹æãŸãã¯æ¯ãšãã
ãããšã奜ãŸããã The temperature at which the reaction of the present invention is carried out is not particularly limited, but is preferably -10°C to 150°C, more preferably 20°C to 80°C. When carrying out the reaction above the boiling point of the solvent, it is necessary to use a pressure vessel. It is also preferred that the reaction mixture be stirred or shaken.
åå¿æéã«å¶éã¯ãªãããïŒåãªãã10æéã
奜ãŸãããããã«ïŒåãªããïŒæéã奜ãŸããã
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ããã Although there is no restriction on the reaction time, it is preferably 1 minute to 10 hours, more preferably 5 minutes to 6 hours.
The reaction rate depends on temperature, type of amine, concentration of raw materials,
The reaction time should be set depending on the conditions, as it is largely controlled by the type of solvent, etc., but during the reaction,
It is recommended that the end time of the reaction be determined by sampling at regular intervals and quantifying the raw materials and products using gas chromatography, liquid chromatography, etc. In order to stop the reaction, it is necessary to deactivate the lithium compound with an alcohol such as methanol or ethanol, water, or the like.
çæç©ã§ããååç©ïŒïŒãåé¢ããã«ã¯ãå
çµæ¶ãã«ã©ã ã¯ãããã°ã©ãã€ãŒãæœåºçã®äžè¬
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žãŸãã¯å¡©åæ°ŽçŽ ã¬ã¹ãå ããããšã«ãããå
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žå¡©ãšããŠæåºãããæ¹æ³ãã
ãã In order to isolate the product compound (), general organic chemical separation methods such as recrystallization, column chromatography, extraction, etc. can be used. There is also a method of precipitating the compound () as a hydrochloride salt by adding hydrochloric acid or hydrogen chloride gas.
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ãã·æš¹èçã®ç¡¬åå€ãšããŠäœ¿çšããããšãã§ã
ãã The compound () obtained by the present invention can be used as a curing agent for epoxy resins and the like.
以äžæ¬çºæã®å®æœäŸã瀺ãããæ¬çºæã¯ããã
ãã®å®æœäŸã®ç¯å²ã«éå®ããããã®ã§ã¯ãªãã Examples of the present invention will be shown below, but the present invention is not limited to the scope of these Examples.
å®æœäŸ ïŒ
å
容ç©800mlã®èå§ã¬ã©ã¹å®¹åšã«ããããªãŠã
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¥ãããExample 1 Tetrahydrofuran 356 dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml.
After adding ml, diethylenetriamine 149g
(1.44 mol) was added, and the inside of the container was purged with nitrogen. Next, 44.6 ml (0.072 mol) of n-butyllithium
74.8g of styrene dried and dehydrated with synthetic zeolite after introducing 15% n-hexane solution
(0.72 mol) was introduced.
åå¿å®¹åšã40âã®æ°Žæ§œã«å
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ïœã®åå¿çæç©ãåŸãã The reaction vessel was placed in a water bath at 40° C., and stirring was continued for 3 hours, and then 100 ml of methanol was added to the reaction mixture to stop the reaction. When acetone was added in Step 5, a precipitate formed, so after removing this, the object was thoroughly washed with acetone and dried in a vacuum dryer.137
g of reaction product was obtained.
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åŸãã This reaction product was further dissolved in methanol (1), added with acetone (5), reprecipitated, filtered, washed with acetone, and dried in a vacuum dryer to yield 126 g (85%). A reaction product was obtained.
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ããåæããçµæã次ã®æ§é ããã€çæç©ã§ãã
ããšãããã€ãã As a result of analyzing this reaction product using a general organic chemical analysis method, it was found that the product had the following structure.
以äžã«åæã®çµæã瀺ãã The results of the analysis are shown below.
å
çŽ åæïŒC69.57ïŒ69.52ïŒãH10.14ïŒ10.21ïŒã
N20.29ïŒ20.27ïŒ
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ã®æ°å€ã¯çè«å€ã瀺ããElemental analysis; C69.57 (69.52), H10.14 (10.21),
N20.29 (20.27) However, the numbers in parentheses here indicate the theoretical values.
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¥ãããMass spectrum (M + /e); 207 (M + ), 130,
102, 77 and other infrared absorption spectra (cm -1 ); 690, 742, 1038,
Around 1360, 1450, 1492, 1601, 2805, 3300 (wide range) Nuclear magnetic resonance spectrum (ÎŽ-value); around 7.2 (multiplet, 5H), 2-3.5 (multiplet, 12H), 1.10 (singlet, 4H) ) Example 2 Tetrohydrofuran 356 dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml.
After adding ml, diethylenetriamine 112g
(1.09 mol) was added, and the inside of the container was purged with nitrogen. Then 45 ml (0.072 mol) of n-butyllithium 15
75 g (0.72 mol) of styrene dried and dehydrated with synthetic zeolite after introducing %n-hexane solution
introduced.
åå¿å®¹åšã20âã®æ°Žæ§œã«å
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ã³èµ€å€ã¹ãã¯ãã«ãã確èªããã The reaction vessel was placed in a 20°C water bath, and stirring was continued for 5 hours. The product was isolated from the reaction mixture in the same manner as in Example 1, yielding 118 g (79%) of a colorless solid. It was confirmed from liquid chromatography and infrared spectroscopy that this substance was the same as the substance obtained in Example 1.
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ã¢ã«ïŒãå°å
¥ãããExample 3 Tetrahydrofuran 356 dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml.
After adding ml, diethylenetriamine 149g
(1.44 mol) was added, and the inside of the container was purged with nitrogen. Next, 29.8 ml (0.048 mol) of n-butyllithium
After introducing a 15% n-hexane solution, 49.9 g (0.48 g) of styrene was dried and dehydrated using synthetic zeolite.
mol) was introduced.
åå¿å®¹åšã60âã®æ°Žæ§œã«å
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ãŠãåå¿ãåæ¢ãããã The reaction container was placed in a water bath at 60° C., and stirring was continued for 2 hours, and then 1 part of methanol was added to the reaction mixture to stop the reaction.
ãã®åå¿æ··åç©ãèžçã«ãããåæã®ã¹ãã¬ã³
ããã³ãžãšãã¬ã³ããªã¢ãã³çãé€ããæ®çç©95
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ïŒã®
åå¿çæç©ãåŸãã This reaction mixture was distilled to remove raw materials such as styrene and diethylenetriamine, leaving a residue of 95%.
g (95%) was obtained. After dissolving this residue in 100ml of methanol and blowing hydrogen chloride gas into it,
This was rejected because a precipitate formed. After adding 400 ml of 4N-NaOH to the obtained product and dissolving it, the mixture was passed through a cation exchange resin and concentrated to obtain 81 g (81%) of a reaction product.
ãã®åå¿çæç©ã¯ã液äœã¯ãããã°ã©ãã€ãŒãš
èµ€å€ã¹ãã¯ãã«ã®çµæãããå®æœäŸïŒãšåäžã®ç
æç©ã§ããããšãããã€ãã This reaction product was found to be the same product as in Example 1 from the results of liquid chromatography and infrared spectroscopy.
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ïœâãããµã³
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¥ããåŸãåæãŒãªã©ã€ãã«ãã也ç¥ã
è±æ°Žããïœâã¯ãã«ã¹ãã¬ã³99.8ïœïŒ0.72ã¢ã«ïŒ
ãå°å
¥ãããExample 4 390 ml of benzene dried and distilled over sodium metal was placed in a pressure-resistant glass container with an internal volume of 800 ml, and then 149 g (1.44 mol) of diethylenetriamine was added, and the inside of the container was purged with nitrogen. Then 45ml (0.072
After introducing a 15% n-hexane solution of n-butyllithium (mol), drying with synthetic zeolite,
Dehydrated p-chlorostyrene 99.8g (0.72mol)
introduced.
åå¿å®¹åšã40âã®æ°Žæ§œã«å
¥ããïŒæéæ¹æãç¶
ããåŸãåå¿æ··åç©ããå®æœäŸïŒãšåæ§ã®æ¹æ³ã«
ãŠåé¢ãã139ïœïŒ80ïŒ
ïŒã®åå¿çæç©ãåŸãã The reaction vessel was placed in a water bath at 40° C., and stirring was continued for 4 hours, followed by isolation from the reaction mixture in the same manner as in Example 1 to obtain 139 g (80%) of the reaction product.
ãã®åå¿çæç©ãäžè¬ã®ææ©ååŠçåææ³ã«ã
ãåæããçµæã次ã®æ§é ããã€çæç©ã§ããã
ãšãããã€ãã As a result of analyzing this reaction product using a general organic chemical analysis method, it was found that the product had the following structure.
以äžã«åæã®çµæã瀺ãã The results of the analysis are shown below.
å
çŽ åæïŒC59.63ïŒ59.62ïŒãH8.28ïŒ8.34ïŒãN17.39
ïŒ17.38ïŒãCl14.70ïŒ14.66ïŒ
ããããæ¬åŒ§å
ã®æ°å€ã¯çè«å€ã瀺ããElemental analysis; C59.63 (59.62), H8.28 (8.34), N17.39
(17.38), Cl14.70 (14.66) However, the numbers in parentheses indicate theoretical values.
ãã¹ã¹ãã¯ãã«ïŒ241ïŒM+ïŒïœ
ïŒã206ïŒïŒâClïŒã
130ïŒïŒâC6H4ClïŒã111ïŒC6H4ClïŒã102
ïŒC4H12N3ïŒ
èµ€å€åžåã¹ãã¯ãã«ïŒcm-1ïŒïŒ690ã742ã830ã
1038ã1360ã1450ã1492ã1601ã2805ã3300ä»
è¿ïŒå¹
åºãïŒä»
å®æœäŸ ïŒ
éæµåšã滎äžããŒãããã³æ¹ææ£ãåãã200
mlã®äžã€å£ãã©ã¹ã³ã«ããããªãŠã éå±ã§è±æ°Žã
ããã³ãŒã³100mlããã³11.6ïœïŒ0.05ã¢ã«ïŒã®ã
ã³ã¿ãšãã¬ã³ãããµãã³ãå
¥ããã容åšå
ãçªçŽ
眮æããåŸã3.1mlïŒ0.005ã¢ã«ïŒã®ïœâããã«ãª
ããŠã ã®15ïŒ
ãããµã³æº¶æ¶²ãæ¹æããªããå ã
ãã次ã«ã7.45ïœïŒ0.05ã¢ã«ïŒã®ã¡ã¿âãããã¹
ãã¬ã³ã30mlã®ãã³ãŒã³ã«ãšãããæ¹æããªãã
滎äžããŒãããçŽ10åããã€ãŠåå¿åšå
ã«å°å
¥ã
ãããã®åŸãçŽïŒæéããã³ãŒã³ã®éæµæž©åºŠã§æ¹
æãç¶ããåŸãåå¿æ··åç©ã«10mlã®ã¡ã¿ããŒã«ã
å ããŠåå¿ãåæ¢ããããåå¿æ··åç©å
šäœã®äœç©
ã®1/10ãæ¿çž®åŸãã«ã©ã ã¯ãããã°ã©ãã€ãŒã«ã
ã€ãŠåé¢ãããšããã0.65ïœïŒæç®ã§34ïŒ
ïŒã®ç
æç©ãåŸãã液äœã¯ãããã°ã©ãã€ãŒã«ãã€ãŠå
æãããšããããã®çæç©ã¯ã»ãåéã¥ã€ã®äºã€
ã®æåã®æ··åç©ã§ããããšãããã€ããåæã®çµ
æããããã®ãã®ã¯ïŒã»14âãžã¢ããâN3âïœïŒ
âïŒïœâãããããšãã«ïŒãšãã«ïœâïŒã»ïŒã»ïŒã»
12âããã©ã¢ã¶âïœâããã©ãã«ã³ïŒïœïŒïŒãïœ
ïŒïŒãŸãã¯ïœïŒïŒãïœïŒïŒïŒããã³ïŒã»14âãžã¢
ããâN6âïœïŒâïŒïœâãããããšãã«ïŒãšãã«ïœ
âïŒã»ïŒã»ïŒã»12âããã©ã¢ã¶âïœâããã©ãã«
ã³ïŒïœïŒïŒãïœïŒïŒãŸãã¯ïœïŒïŒãïœïŒïŒïŒã§ã
ãããšãããã€ããåæçµæã¯äžèšã®ãšããã§ã
ããMass spectrum; 241 (M + /e), 206 (M-Cl),
130 (M-C 6 H 4 Cl), 111 (C 6 H 4 Cl), 102
(C 4 H 12 N 3 ) Infrared absorption spectrum (cm -1 ); 690, 742, 830,
1038, 1360, 1450, 1492, 1601, 2805, around 3300 (wide range) and others Example 5 200 equipped with a reflux vessel, dropping funnel and stirring bar
100 ml of benzene dehydrated over sodium metal and 11.6 g (0.05 mol) of pentaethylenehexamine are placed in a 3-necked flask. After purging the inside of the container with nitrogen, 3.1 ml (0.005 mol) of a 15% hexane solution of n-butyllithium was added with stirring. Next, 7.45 g (0.05 mol) of meta-nitrostyrene was dissolved in 30 ml of benzene and introduced into the reactor through the dropping funnel for about 10 minutes while stirring. After that, stirring was continued for about 8 hours at the reflux temperature of benzene, and then 10 ml of methanol was added to the reaction mixture to stop the reaction. After concentrating 1/10 of the total volume of the reaction mixture and separating it by column chromatography, 0.65 g (calculated as 34%) of the product was obtained. Analysis by liquid chromatography showed that the product was a mixture of two components in approximately equal amounts. As a result of analysis, these substances are 1,14-diamino-N 3 -{2
-(m-nitrophenyl)ethyl}-3.6.9.
12-tetraaza-n-tetradecane (m=1, n
=4 or m=4, n=1) and 1,14-diamino- N6- {2-(m-nitrophenyl)ethyl}
It was found to be -3,6,9,12-tetraaza-n-tetradecane (m=2, n=3 or m=3, n=2). The analysis results are as follows.
å
çŽ åæïŒC56.42ïŒ56.67ïŒãH9.29ïŒ9.25ïŒãN25.98
ïŒ25.70ïŒ
èµ€å€åžåã¹ãã¯ãã«ïŒåäœcm-1ïŒïŒ742ã830ã
1038ã1332ã1450ã1530ã1601ã2805ã3300ä»
è¿ïŒå¹
åºãïŒä»
å®æœäŸ ïŒ
éæµåšã滎äžããŒãããã³æµåãã©ãã€ã³ã§ã·
ãŒã«ãããæ¹ææ£ãåãã200mlã®äžã€å£ãã©ã¹
ã³ã«ã100mlã®è±æ°Žãã³ãŒã³ããã³8.03ïœïŒ0.055
ã¢ã«ïŒã®ããªãšãã¬ã³ããã©ãã³ãå
¥ããåŸã泚
å°åšã§3.1mlïŒ0.005ã¢ã«ïŒã®ïœâããã«ãªããŠã
ã®15ïŒ
ãããµã³æº¶æ¶²ãæ¹æããªããå ããã次
ã«ã8.0ïœïŒ0.05ã¢ã«ïŒã®ãã©âïœâããã«ã¹ã
ã¬ã³ã30mlã®ãã³ãŒã³ã«ãšããã滎äžããŒããã
å ããããã³ãŒã³ã®éæµæž©åºŠã§ïŒæéæ¹æãç¶ã
ãåŸãïŒmlã®ã¡ã¿ããŒã«ã§åå¿ãåæ¢ããããå®
æœäŸïŒãšåæ§ã®ææ³ã«ãŠ1.09ïœïŒæç®ã§71ïŒ
ïŒã®
çæç©ãåŸãã液äœã¯ãããã°ã©ãã€ãŒã«ãã€ãŠ
åæãããšããããã®çæç©ã¯åäžã®æåããæ
ã€ãŠããããšãããã€ããäžèšã®åæçµæããã
ãã®ãã®ã¯ïŒã»ïŒâãžã¢ããâN3âïœïŒâïŒãã©
âïœâããã«ïŒãšãã«ïœâïŒã»ïŒâãžã¢ã¶âïœâ
ãªã¯ã¿ã³ã§ããããšãããã€ããåæçµæã¯äžèš
ã®ãšããã§ãããElemental analysis; C56.42 (56.67), H9.29 (9.25), N25.98
(25.70) Infrared absorption spectrum (unit cm -1 ); 742, 830,
Around 1038, 1332, 1450, 1530, 1601, 2805, 3300 (wide range) and others Example 6 100 ml of dehydrated benzene was placed in a 200 ml three-necked flask equipped with a reflux, dropping funnel, and a stirring bar sealed with liquid paraffin. and 8.03g (0.055
mol) of triethylenetetramine was added, and then 3.1 ml (0.005 mol) of a 15% hexane solution of n-butyllithium was added with stirring using a syringe. Next, 8.0 g (0.05 mol) of para-n-butylstyrene was dissolved in 30 ml of benzene and added through the dropping funnel. After continued stirring for 8 hours at the reflux temperature of benzene, the reaction was stopped with 2 ml of methanol. In the same manner as in Example 5, 1.09 g (71% in terms of conversion) of a product was obtained. Analysis by liquid chromatography showed that the product consisted of a single component. From the analysis results below,
This product is 1,8-diamino-N 3 -{2-(para-n-butyl)ethyl}-3,6-diaza-n-
Turns out it's octane. The analysis results are as follows.
å
çŽ åæïŒC70.31ïŒ70.54ïŒãH11.35ïŒ11.18ïŒã
N18.45ïŒ18.28ïŒ
èµ€å€åžåã¹ãã¯ãã«ïŒåäœcm-1ïŒïŒ742ã830ã
1038ã1450ã1601ã2804ã3300ä»è¿ïŒå¹
åºãïŒ
ä»Elemental analysis; C70.31 (70.54), H11.35 (11.18),
N18.45 (18.28) Infrared absorption spectrum (unit cm -1 ); 742, 830,
Around 1038, 1450, 1601, 2804, 3300 (wide range)
other
Claims (1)
åºãããã²ã³ãŸãã¯ãããåºãïœããã³ïœã¯ïŒã
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ã®ç¯å²ç¬¬ïŒé èšèŒã®å¡©åºæ§ååç©ã ïŒ ïŒžãæ°ŽçŽ ãã¡ãã«åºããšãã«åºãŸãã¯ã¯ãã«
ã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé ãŸãã¯ç¬¬ïŒé èšèŒã®
å¡©åºæ§ååç©ã ïŒ æ§é åŒïŒïŒ ïŒåŒäžãïœããã³ïœã¯ïŒããïŒã®æŽæ°ãè¡šãããïŒ ã§ç€ºãããã¢ãã³ããããã«å¯Ÿå¿ããæ§é åŒ
ïŒïŒ ïŒåŒäžãïœããã³ïœã¯ïŒããïŒã®æŽæ°ãè¡šãããïŒ ã§ç€ºãããã¢ã«ã«ãªéå±ã¢ããã®å ±åäžã«ãæ§é
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城ãšããæ§é åŒïŒïŒ ïŒåŒäžãã¯æ°ŽçŽ ãççŽ æ°ïŒããïŒã®ã¢ã«ãã«
åºãããã²ã³ãŸãã¯ãããåºãïœããã³ïœã¯ïŒã
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ãããçšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®å¡©åºæ§
ååç©ã®è£œé æ³ã ïŒ æ§é åŒïŒïŒã§ç€ºãããã¢ãã³ãšã¢ã«ãã«ãª
ããŠã ãã調補ãããªããŠã ã¢ãããçšããç¹èš±
è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®å¡©åºæ§ååç©ã®è£œé æ³ã ïŒ ã¢ã«ãã«ãªããŠã ãšããŠïœâããã«ãªããŠã
ãçšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®å¡©åºæ§åå
ç©ã®è£œé æ³ã ïŒ äžæŽ»æ§ææ©æ¶²äœã®å ±åäžã«åå¿ãè¡ãªãç¹èš±
è«æ±ã®ç¯å²ç¬¬ïŒé ãªãã第ïŒé ã®ããããã«èšèŒ
ã®å¡©åºæ§ååç©ã®è£œé æ³ã ïŒ äžæŽ»æ§ææ©æ¶²äœãšããŠãããµã³ãã·ã¯ããã
ãµã³ãããã©ããããã©ã³ããšãŒãã«ããã³ãŒ
ã³ããã«ãšã³ã®ããããããŸãã¯ïŒçš®ä»¥äžã®æ··å
ç©ãçšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®å¡©åºæ§å
åç©ã®è£œé æ³ã ïŒïŒ æ§é åŒïŒïŒã§ç€ºãããã¢ãã³ãšã¢ã«ãã«
ãªããŠã ã®æ··åç©ã«ã¹ãã¬ã³çœ®æäœïŒïŒãå ã
ãç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé ãªãã第ïŒé ã®ãããã
ã«èšèŒã®å¡©åºæ§ååç©ã®è£œé æ³ã[Claims] 1 Structural formula () (wherein, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4). 2. The basic compound according to claim 1, wherein (m+n) is an integer from 2 to 5. 3. The basic compound according to claim 1 or 2, wherein X is hydrogen, methyl group, ethyl group, or chloro. 4 Structural formula () (In the formula, m and n represent integers from 1 to 4.) An amine represented by the corresponding structural formula () (In the formula, m and n represent integers from 1 to 4.) In the coexistence of an alkali metal amide represented by the structural formula () (In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen, or a nitro group.) (In the formula, X represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a halogen or a nitro group, and m and n represent integers of 1 to 4.) 5. The method for producing a basic compound according to claim 4, using lithium amide as the alkali metal amide (). 6. A method for producing a basic compound according to claim 4, using a lithium amide prepared from an amine represented by the structural formula () and an alkyl lithium. 7. The method for producing a basic compound according to claim 4, using n-butyllithium as the alkyllithium. 8. A method for producing a basic compound according to any one of claims 4 to 7, wherein the reaction is carried out in the presence of an inert organic liquid. 9. The method for producing a basic compound according to claim 8, wherein any one of hexane, cyclohexane, tetrahydrofuran, ether, benzene, toluene, or a mixture of two or more thereof is used as the inert organic liquid. 10. The method for producing a basic compound according to any one of claims 4 to 9, which comprises adding a styrene substitute () to a mixture of an amine represented by the structural formula () and an alkyl lithium.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9666579A JPS5620552A (en) | 1979-07-31 | 1979-07-31 | Novel basic compound and its preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9666579A JPS5620552A (en) | 1979-07-31 | 1979-07-31 | Novel basic compound and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5620552A JPS5620552A (en) | 1981-02-26 |
JPS636540B2 true JPS636540B2 (en) | 1988-02-10 |
Family
ID=14171102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9666579A Granted JPS5620552A (en) | 1979-07-31 | 1979-07-31 | Novel basic compound and its preparation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5620552A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW539661B (en) * | 2000-09-12 | 2003-07-01 | Mitsubishi Gas Chemical Co | Amino compound and process for producing the same |
JP4797345B2 (en) * | 2003-08-13 | 2011-10-19 | äžè±çŠæ¯ååŠæ ªåŒäŒç€Ÿ | Method for producing amino composition |
-
1979
- 1979-07-31 JP JP9666579A patent/JPS5620552A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5620552A (en) | 1981-02-26 |
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