KR20150018837A - Method for producing phosphoric acid ester amides - Google Patents
Method for producing phosphoric acid ester amides Download PDFInfo
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- KR20150018837A KR20150018837A KR20147036268A KR20147036268A KR20150018837A KR 20150018837 A KR20150018837 A KR 20150018837A KR 20147036268 A KR20147036268 A KR 20147036268A KR 20147036268 A KR20147036268 A KR 20147036268A KR 20150018837 A KR20150018837 A KR 20150018837A
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- South Korea
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- -1 phosphoric acid ester amides Chemical class 0.000 title claims abstract description 186
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 26
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 18
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims description 66
- 125000000217 alkyl group Chemical group 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 54
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 239000007810 chemical reaction solvent Substances 0.000 claims description 30
- 125000003342 alkenyl group Chemical group 0.000 claims description 29
- 125000001424 substituent group Chemical group 0.000 claims description 29
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 26
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 19
- 125000002947 alkylene group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 125000004429 atom Chemical group 0.000 claims description 10
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 74
- 239000011541 reaction mixture Substances 0.000 description 26
- 238000002844 melting Methods 0.000 description 20
- 230000008018 melting Effects 0.000 description 20
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 18
- 229910000039 hydrogen halide Inorganic materials 0.000 description 17
- 239000012433 hydrogen halide Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- AMAHHZOOPQPKRY-UHFFFAOYSA-N anilino diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)ONC1=CC=CC=C1 AMAHHZOOPQPKRY-UHFFFAOYSA-N 0.000 description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 11
- 0 *N([Al])P(*)(O)=O Chemical compound *N([Al])P(*)(O)=O 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N c(cc1)cc2c1cccc2 Chemical compound c(cc1)cc2c1cccc2 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229940018564 m-phenylenediamine Drugs 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- BLAOQYUKUBIXCF-UHFFFAOYSA-N 1-dichlorophosphoryloxynaphthalene Chemical compound C1=CC=C2C(OP(Cl)(=O)Cl)=CC=CC2=C1 BLAOQYUKUBIXCF-UHFFFAOYSA-N 0.000 description 2
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical class OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- NVIUJBDCLBPBPA-UHFFFAOYSA-N 1-[chloro(naphthalen-1-yloxy)phosphoryl]oxynaphthalene Chemical compound C1=CC=C2C(OP(=O)(OC=3C4=CC=CC=C4C=CC=3)Cl)=CC=CC2=C1 NVIUJBDCLBPBPA-UHFFFAOYSA-N 0.000 description 1
- IHILHBFGMHPCDV-UHFFFAOYSA-N 1-[chloro-(2-phenylphenoxy)phosphoryl]oxy-2-phenylbenzene Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(=O)(Cl)OC1=CC=CC=C1C1=CC=CC=C1 IHILHBFGMHPCDV-UHFFFAOYSA-N 0.000 description 1
- UWOKONWYYPRXCH-UHFFFAOYSA-N 1-[chloro-(2-propan-2-ylphenoxy)phosphoryl]oxy-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1OP(Cl)(=O)OC1=CC=CC=C1C(C)C UWOKONWYYPRXCH-UHFFFAOYSA-N 0.000 description 1
- VYHGCXOQLBEEJN-UHFFFAOYSA-N 1-[chloro-(3,5-dimethylphenoxy)phosphoryl]oxy-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(OP(Cl)(=O)OC=2C=C(C)C=C(C)C=2)=C1 VYHGCXOQLBEEJN-UHFFFAOYSA-N 0.000 description 1
- QSHGXOAKDDJDGG-UHFFFAOYSA-N 1-[chloro-(3-methylphenoxy)phosphoryl]oxy-3-methylbenzene Chemical compound CC1=CC=CC(OP(Cl)(=O)OC=2C=C(C)C=CC=2)=C1 QSHGXOAKDDJDGG-UHFFFAOYSA-N 0.000 description 1
- BNDUYVNXBZYPMZ-UHFFFAOYSA-N 1-[chloro-(4-methylphenoxy)phosphoryl]oxy-4-methylbenzene Chemical compound C1=CC(C)=CC=C1OP(Cl)(=O)OC1=CC=C(C)C=C1 BNDUYVNXBZYPMZ-UHFFFAOYSA-N 0.000 description 1
- DHDKHEFRFQLNCX-UHFFFAOYSA-N 1-dichlorophosphoryloxy-2-phenylbenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1C1=CC=CC=C1 DHDKHEFRFQLNCX-UHFFFAOYSA-N 0.000 description 1
- FZYHTHFEIUVTNL-UHFFFAOYSA-N 1-dichlorophosphoryloxy-3,5-dimethylbenzene Chemical compound CC1=CC(C)=CC(OP(Cl)(Cl)=O)=C1 FZYHTHFEIUVTNL-UHFFFAOYSA-N 0.000 description 1
- XSUSEDGKQCJMBW-UHFFFAOYSA-N 1-dichlorophosphoryloxy-3-methylbenzene Chemical compound CC1=CC=CC(OP(Cl)(Cl)=O)=C1 XSUSEDGKQCJMBW-UHFFFAOYSA-N 0.000 description 1
- YGXDFNYVQUNFEB-UHFFFAOYSA-N 1-dichlorophosphoryloxy-3-phenylbenzene Chemical compound C1(=CC(=CC=C1)OP(=O)(Cl)Cl)C1=CC=CC=C1 YGXDFNYVQUNFEB-UHFFFAOYSA-N 0.000 description 1
- DXOJYMMUNCDFHT-UHFFFAOYSA-N 1-dichlorophosphoryloxy-4-phenylbenzene Chemical compound C1=CC(OP(Cl)(=O)Cl)=CC=C1C1=CC=CC=C1 DXOJYMMUNCDFHT-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- UOTCTDSGHIMHTA-UHFFFAOYSA-N 1-piperazin-1-ylethanamine Chemical class CC(N)N1CCNCC1 UOTCTDSGHIMHTA-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- WXCXJSOCIOHPLT-UHFFFAOYSA-N 2-[chloro-(2,6-dimethylphenoxy)phosphoryl]oxy-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1OP(Cl)(=O)OC1=C(C)C=CC=C1C WXCXJSOCIOHPLT-UHFFFAOYSA-N 0.000 description 1
- NDBIDPWNTMLXFU-UHFFFAOYSA-N 2-dichlorophosphoryloxy-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(OP(Cl)(Cl)=O)=C1 NDBIDPWNTMLXFU-UHFFFAOYSA-N 0.000 description 1
- UOJIWWGEVGBWBD-UHFFFAOYSA-N 2-dichlorophosphoryloxynaphthalene Chemical compound C1=CC=CC2=CC(OP(Cl)(=O)Cl)=CC=C21 UOJIWWGEVGBWBD-UHFFFAOYSA-N 0.000 description 1
- PGCRDIRKSWIOPB-UHFFFAOYSA-N 2-methyl-2,3-dihydro-1h-imidazole Chemical compound CC1NC=CN1 PGCRDIRKSWIOPB-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical compound NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- HUVGUCFNIKUOTI-UHFFFAOYSA-N 4-[1,1-bis(4-aminophenyl)propyl]aniline Chemical compound C=1C=C(N)C=CC=1C(C=1C=CC(N)=CC=1)(CC)C1=CC=C(N)C=C1 HUVGUCFNIKUOTI-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-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
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MJWBBMIXGHSVKK-UHFFFAOYSA-N C1(=CC=CC=C1)C=C1C(C=CC=C1)C(C1=CC=CC=C1)=C=CC1=CC=CC=C1 Chemical group C1(=CC=CC=C1)C=C1C(C=CC=C1)C(C1=CC=CC=C1)=C=CC1=CC=CC=C1 MJWBBMIXGHSVKK-UHFFFAOYSA-N 0.000 description 1
- BZDYQGCCARCERQ-UHFFFAOYSA-N CC(C)(C=C1)C=[I]C=C1NP(Oc1ccccc1)(Oc1ccccc1)=O Chemical compound CC(C)(C=C1)C=[I]C=C1NP(Oc1ccccc1)(Oc1ccccc1)=O BZDYQGCCARCERQ-UHFFFAOYSA-N 0.000 description 1
- JLBJTIZZUNUXTC-UHFFFAOYSA-N CC(C)CCl(C1=CC=CC=C1)P(=O)(O)Cl Chemical compound CC(C)CCl(C1=CC=CC=C1)P(=O)(O)Cl JLBJTIZZUNUXTC-UHFFFAOYSA-N 0.000 description 1
- ZLQJASGQANYGJB-UHFFFAOYSA-N CC1(c2ccccc2C=CC=C1)OP(NC1CCOCC1)(NC1CCOCC1)=O Chemical compound CC1(c2ccccc2C=CC=C1)OP(NC1CCOCC1)(NC1CCOCC1)=O ZLQJASGQANYGJB-UHFFFAOYSA-N 0.000 description 1
- ADQDTIAWIXUACV-UHFFFAOYSA-N CCCc1ccc(CC)cc1 Chemical compound CCCc1ccc(CC)cc1 ADQDTIAWIXUACV-UHFFFAOYSA-N 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N CCCc1ccccc1 Chemical compound CCCc1ccccc1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SQPVQGHHSGWUEP-UHFFFAOYSA-N O.[P] Chemical compound O.[P] SQPVQGHHSGWUEP-UHFFFAOYSA-N 0.000 description 1
- FZNQHYXSPNEFAI-UHFFFAOYSA-N O=P(Nc1ccccc1)(Oc1ccccc1)Oc1ccccc1 Chemical compound O=P(Nc1ccccc1)(Oc1ccccc1)Oc1ccccc1 FZNQHYXSPNEFAI-UHFFFAOYSA-N 0.000 description 1
- FCNNTNZMTKXXAG-UHFFFAOYSA-N OCCNP(N1CCOCC1)(Oc1ccccc1)=O Chemical compound OCCNP(N1CCOCC1)(Oc1ccccc1)=O FCNNTNZMTKXXAG-UHFFFAOYSA-N 0.000 description 1
- OKFISLDGFOKWCB-UHFFFAOYSA-N P(=O)(OC1=C(C=CC=C1)CC(C)C)(OC1=C(C=CC=C1)CC(C)C)Cl Chemical compound P(=O)(OC1=C(C=CC=C1)CC(C)C)(OC1=C(C=CC=C1)CC(C)C)Cl OKFISLDGFOKWCB-UHFFFAOYSA-N 0.000 description 1
- NDOUPIIACDKPOV-UHFFFAOYSA-N P(=O)(ONC1=CC=CC=C1)(OC1=C(C=CC=C1C)C)OC1=C(C=CC=C1C)C Chemical compound P(=O)(ONC1=CC=CC=C1)(OC1=C(C=CC=C1C)C)OC1=C(C=CC=C1C)C NDOUPIIACDKPOV-UHFFFAOYSA-N 0.000 description 1
- YRHLBDXPVLKEFH-UHFFFAOYSA-N P(OC1=CC2=CC=CC=C2C=C1)(OC1=CC2=CC=CC=C2C=C1)(=O)Cl Chemical compound P(OC1=CC2=CC=CC=C2C=C1)(OC1=CC2=CC=CC=C2C=C1)(=O)Cl YRHLBDXPVLKEFH-UHFFFAOYSA-N 0.000 description 1
- WCKVFZXCNOYOSE-UHFFFAOYSA-N P1(OCC2=CC(=CC=C2)CO1)(=O)Cl Chemical compound P1(OCC2=CC(=CC=C2)CO1)(=O)Cl WCKVFZXCNOYOSE-UHFFFAOYSA-N 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- WPHKUISZYSINAP-UHFFFAOYSA-N [butyl(phenyl)-lambda3-chloranyl]-chlorophosphinic acid Chemical compound CCCCCl(C1=CC=CC=C1)P(=O)(O)Cl WPHKUISZYSINAP-UHFFFAOYSA-N 0.000 description 1
- DABXJIMFYFHWSP-UHFFFAOYSA-N [tert-butyl(phenyl)-lambda3-chloranyl]-chlorophosphinic acid Chemical compound CC(C)(C)Cl(C1=CC=CC=C1)P(=O)(O)Cl DABXJIMFYFHWSP-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UQMSNGHNDCUPET-UHFFFAOYSA-N chloro-[phenyl(propan-2-yl)-lambda3-chloranyl]phosphinic acid Chemical compound CC(C)Cl(C1=CC=CC=C1)P(=O)(O)Cl UQMSNGHNDCUPET-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- KUBCHQZSJRHFIV-UHFFFAOYSA-N dianilino phenyl phosphate Chemical compound C=1C=CC=CC=1NOP(OC=1C=CC=CC=1)(=O)ONC1=CC=CC=C1 KUBCHQZSJRHFIV-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- SXADIBFZNXBEGI-UHFFFAOYSA-N phosphoramidous acid Chemical group NP(O)O SXADIBFZNXBEGI-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical class NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2462—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of unsaturated acyclic amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2475—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aralkylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
According to the present invention, phosphorammonohalidates are dehydrohalogenated with an amine compound having one or two primary amino groups and / or secondary amino groups in the molecule to correspond to the phosphomonohalidates Wherein the reaction is carried out by reacting the phosphoromonohalidate and the amine compound at a temperature of 130 ° C or higher without excess use of an amine compound for the phosphorohalidate, Method is provided.
Description
The present invention relates to a novel process for preparing phosphoric acid ester amides.
Phosphoric acid ester amides are used, for example, as flame retardants in molded products of synthetic resins and fiber products (see, for example, Patent Document 1).
For example, anilino diphenylphosphate, which is a representative example of phosphoric acid ester amides, can be usually obtained by a condensation reaction of diphenylphosphorochloridate and aniline, that is, a dehydrochlorination reaction.
In this reaction, when one equivalent of diphenylphosphorochloridate and aniline are used together, 0.5 equivalent of aniline is reacted with 0.5 equivalent of diphenylphosphorochloridate to produce the desired anilinodiphenylphosphate , And 0.5 equivalent of the remaining aniline acts as a hydrogen chloride capturing agent to form a hydrochloride salt, so 0.5 equivalent of diphenylphosphorochloridate remains unreacted.
Therefore, when anilinodiphenyl phosphate is produced by the reaction of diphenylphosphorochloridate and aniline, usually 2 equivalents of aniline is used per 1 equivalent of diphenylphosphorochloridate, of which aniline 1 equivalent of the aniline is reacted with 1 equivalent of diphenylphosphorochloridate, and 1 equivalent of the remaining aniline acts as a hydrogen chloride scavenger, thereby making effective use of diphenylphosphorochloridate in the reaction (see, for example, Patent Document 2).
However, in the production of anilino diphenyl phosphate, when 2 equivalents of aniline are used per 1 equivalent of diphenylphosphorochloridate and 1 equivalent of aniline is used as a hydrogen chloride capturing agent, anilino di The yield of phenyl phosphate is not more than 50% with respect to aniline. On the other hand, the step of neutralizing and purifying aniline hydrochloride after completion of the reaction is also troublesome, and therefore, the above method is economically disadvantageous in view of aniline .
Therefore, as a hydrogen chloride capturing agent, a heterocyclic aromatic amine compound such as pyridine or an aliphatic tertiary amine such as triethylamine is used instead of aniline (see, for example, Patent Document 3). However, these amines may not effectively function as a hydrogen chloride capturing agent in the case of aromatic amines. In addition, complicated steps are also required to recover and reuse amines from the hydrochloride salts after the completion of the reaction. In addition, according to this method, an odor caused by an amine used in an obtained anilinodiphenyl phosphate may remain.
DISCLOSURE OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems in the production of conventional phosphate ester amides, and it is an object of the present invention to provide a phosphoric acid ester amide having a desired phosphoric acid ester amide And a novel process for producing phosphoric acid ester amides which can be obtained at a high yield relative to the amine compound.
Particularly, the present invention relates to the use of an amine compound represented by the following formula (1) in an amount of from 0.5 equivalents to 2.0 equivalents, and preferably from 0.8 equivalents to 1.2 equivalents, of the amine compound relative to 1 equivalent of phosphorochloridates Which can be obtained in a high yield relative to the amine compound.
According to the present invention,
(A) a compound represented by the general formula (Ia)
≪ RTI ID = 0.0 > phosphomonohalides < / RTI >
In general formula (Ib)
Phosphododihalidates < RTI ID = 0.0 >
(Wherein R 1 , R 2 and R 3 are each independently an alkyl, cycloalkyl, aryl or arylalkyl group which may have a substituent which is inactive in the reaction, And X represents a halogen atom,
At least one amine compound selected from a monoamine compound having one primary amino group and / or secondary amino group in the molecule and a diamine compound having two primary amino groups and / or secondary amino groups in the molecule and Dehydrohalogenation reaction, or
(B) a phospholodihalidate as the phosphohaloylidate is dehydrohalogenated with a monoamine compound having one primary amino group and / or secondary amino group in the molecule, In the process for producing a phosphoric acid ester amide,
Comprising reacting the phosphorohalidates with the amine compound at a temperature of at least < RTI ID = 0.0 > 130 C. < / RTI >
According to the present invention, an aromatic monoamine compound or an aliphatic monoamine compound is used in the dehydrohalogenation reaction of the phosphoramonohalide represented by the general formula (Ia) with a monoamine compound.
According to the present invention, an aromatic diamine compound or an aliphatic diamine compound is used in dehydrohalogenation reaction of the phosphorammonohalidate represented by the general formula (Ia) with a diamine compound.
Further, according to the present invention, an aromatic monoamine compound or an aliphatic monoamine compound is used in dehydrohalogenation reaction of the phosphorodihalidate represented by the general formula (Ib) with a monoamine compound.
That is, according to the present invention, as a preferred embodiment, the following six methods are provided.
(1) The phosphorammonohalidates represented by the general formula (Ia) and the amine compounds represented by the general formula (IIa)
(Wherein, Ar 1 represents an aryl group, Y 1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an arylalkyl group, when Y 1 aryl date, Y 1 is may be the same as Ar 1 (VIa) may be reacted with an aromatic monoamine compound represented by the general formula (VIa)
Lt; RTI ID = 0.0 > (II) < / RTI >
(2) The phosphorammonohalidates represented by the general formula (Ia) and the amine compounds represented by the general formula (IIb)
(Wherein, Ar 2 represents a divalent group containing an aromatic ring, each of which in combination with the two nitrogen atoms in the molecule, Y 2 and Y 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group Or an arylalkyl group, and Y 2 and Y 3 may be the same or different) to react with an aromatic diamine compound represented by the general formula (VIb)
Lt; RTI ID = 0.0 > (II) < / RTI >
(3) The phosphorammonohalide represented by the general formula (Ia) and the compound represented by the general formula (IVa)
(Wherein, Ay 1 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, Y 4 is by a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, or Ay 1 and Y 4 are Co, 5 In this case, the ring may contain an oxygen atom and / or a nitrogen atom as an atom forming the ring. When the atom forming the ring is a nitrogen atom, the nitrogen atom may be substituted with an oxygen atom and / (VIIa) is reacted with an aliphatic monoamine compound represented by the general formula (VIIa)
Lt; RTI ID = 0.0 > (II) < / RTI >
(4) The phosphorammonohalidates represented by the general formula (Ia) and the amine compounds represented by the general formula (IVb)
(Wherein Ay 2 represents an alkylene group or a cycloalkylene group which may have an aromatic group on the carbon atom or between carbon atoms, Y 5 and Y 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, Or Ay 2 and Y 5 may jointly form a 5-membered to 7-membered ring, or Ay 2 and Y 6 may jointly form a 5-membered to 7-membered ring, or Ay 2 and Y 5 may form a 5- And Y < 6 > may form a 5-membered to 7-membered ring together with the aliphatic diamine compound represented by the general formula (VIIb)
Lt; RTI ID = 0.0 > (II) < / RTI >
(5) The phosphorodihalidates represented by the general formula (Ib) and the amine compound represented by the general formula (IIa)
(Wherein, Ar 1 represents an aryl group, Y 1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an arylalkyl group, when Y 1 aryl date, Y 1 is may be the same as Ar 1 (VIIIa) may be reacted with an aromatic monoamine compound represented by the general formula (VIIIa)
Lt; RTI ID = 0.0 > (II) < / RTI >
(6) The phosphorodihalidates represented by the above general formula (Ib) and the amine compounds represented by the general formula (IVa)
(Wherein, Ay 1 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, Y 4 is by a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, or Ay 1 and Y 4 are Co, 5 In this case, the ring may contain an oxygen atom and / or a nitrogen atom as an atom forming the ring. When the atom forming the ring is a nitrogen atom, the nitrogen atom may be substituted with an oxygen atom and / (VIIIb) is reacted with an aliphatic monoamine compound represented by the general formula
Lt; RTI ID = 0.0 > (II) < / RTI >
According to the present invention, in the above-mentioned method, it is preferable to react the amine compound in an amount of 0.5 equivalents or more and less than 2 equivalents, particularly 0.8 equivalents to 1.2 equivalents, per equivalent of phosphorohalide.
According to the present invention, in the above-described method, although the reaction solvent is not necessarily used, it is preferable to use a reaction solvent in order to proceed the reaction smoothly. In this case, . As the reaction solvent having a boiling point of 130 캜 or higher, at least one species selected from aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons and aromatic ethers having a boiling point of 130 캜 or higher is preferably used.
According to the method of the present invention, the above-mentioned amine compound is not used excessively, that is, 0.5 equivalents or more and less than 2 equivalents, preferably 0.8 equivalents to 1.2 equivalents are used for phosphorohalidates, Can be obtained in a high yield relative to the amine compound.
The method for producing phosphoric acid ester amides according to the present invention comprises:
(A) a compound represented by the general formula (Ia)
≪ RTI ID = 0.0 > phosphomonohalides < / RTI >
In general formula (Ib)
Phosphododihalidates < RTI ID = 0.0 >
(Wherein R 1 , R 2 and R 3 are each independently an alkyl, cycloalkyl, aryl or arylalkyl group which may have a substituent which is inactive in the reaction, And X represents a halogen atom,
At least one amine compound selected from a monoamine compound having one primary amino group and / or secondary amino group in the molecule and a diamine compound having two primary amino groups and / or secondary amino groups in the molecule and Dehydrohalogenation reaction, or
(B) a phospholodihalidate as the phosphohaloylidate is dehydrohalogenated with a monoamine compound having one primary amino group and / or secondary amino group in the molecule, In the process for producing a phosphoric acid ester amide,
And reacting the phosphorohalidate with the amine compound at a temperature of 130 ° C or higher.
In the present invention, in the phosphorohalidates represented by the general formulas (Ia) and (Ib), R 1 , R 2 and R 3 are each independently an alkyl group which may have a substituent which is inert to the reaction, An alkyl group, an aryl group or an arylalkyl group, and X represents a halogen atom.
In the present invention, the substituent which is inert to the reaction means a substituent which is not involved in the reaction of the phosphorohalidate and the amine compound according to the present invention, and examples thereof include an alkoxy group such as methoxy group, a nitro group, , A halogen atom such as a chlorine atom, and a heterocyclic group which does not participate in the reaction of the phosphorohalidate and the amine compound according to the present invention. Hereinafter, the same applies.
The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 6 carbon atoms, and the alkyl group having 3 or more carbon atoms may be either linear or branched Examples of such an alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and dodecyl.
The cycloalkyl group is a cycloalkyl group having a total of 5 to 20 carbon atoms, preferably 5 to 12 carbon atoms, which may have an alkyl group as a substituent on the carbon atom forming the ring, and specific examples thereof include cyclopentyl, methylcyclo Pentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl and the like.
The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and is preferably an alkyl group as a substituent on the aromatic ring, preferably an alkyl group having 1 to 6 carbon atoms, and / Or may have one or more substituents which are inactive to the substituent. Accordingly, examples of such aryl groups include phenyl, tolyl, xylanyl, trimethylphenyl, methoxyphenyl, naphthyl, methylnaphthyl, biphenylyl and methylbiphenyl groups.
Examples of the arylalkyl group include a benzyl group and a phenylethyl group. The arylalkyl group may also have an alkyl group of 1 to 6 carbon atoms on the aromatic ring or a substituent which is inert to the reaction as described above.
In the phosphoro halide, the halogen atom (X) is a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. That is, in the present invention, the phosphohaloylidate is preferably a phosphorochloridate.
Particularly, in the present invention, preferably, in the phosphorohalidates represented by the general formulas (Ia) and (Ib), R 1 , R 2 and R 3 each independently represent a carbon atom An alkyl group having a number of 1 to 6 or an aryl group which may have a substituent which is inert to the reaction as described above, particularly preferably a phenyl group, a tolyl group or a xylylenyl group, and X is a chlorine atom.
Accordingly, in the present invention, preferred specific examples of the phosphorammonohalidates represented by the general formula (Ia) include diphenyl phosphorochloridate, di (m-tolyl) phosphorochloridate, Di (p-tolyl) phosphorochloridate, di (2,6-xylenyl) phosphorochloridate, di (3,5-xylenyl) phosphorochloridate, Bis (isopropylphenyl) phosphorochloridate, bis (isobutylphenyl) phosphorochloridate, bis (t-butylphenyl) phosphochloridate, bis ) Phosphochloridate, di-1-naphthylphosphorochloridate, di-2-naphthylphosphorochloridate, di-2-biphenylylphosphorochloridate, di- Di-4-biphenylylphosphorochloridate and the like, and mixtures of any two or more thereof.
Further, as preferred specific examples of the phosphorodihalidylate represented by the general formula (Ib), for example, phenylphosphorodichloridate, m-tolylphosphorodichloridate, p-tolylphosphorodichloro Xylylenylphosphorodichloridate, 3,5-xylenylphosphorodichloridate, 2,5-xylenylphosphorodichloridate, and the like, Butylphenylphosphorodichloridate, 1-naphthylphosphorodichloridate, isopropylphenylphosphorodichloridate, isobutylphenylphosphorodichloridate, t-butylphenylphosphorodichloridate, 1-naphthylphosphorodichloridate, 2- Naphthylphosphorodichloridate, 2-biphenylylphosphorodichloridate, 3-biphenylylphosphorodichloridate, and 4-biphenylylphosphorodichloridate.
According to the present invention, these phosphoramonohalides can be prepared by reacting a monoamine compound having one primary amino group and / or secondary amino group in the molecule with two primary amino groups and / or secondary amino groups in the molecule , A desired dehydrohalogenation reaction, that is, a condensation reaction with the at least one amine compound selected from a diamine compound having a phosphoramidite group, .
Further, according to the present invention, when the above-described phosphorodihalidates are used as a phosphohalidate, they may be added to a monoamine compound having one primary amino group and / or secondary amino group in the molecule, By the hydrogen halide reaction, that is, the condensation reaction, desired phosphoric acid ester amides can be obtained corresponding to the phosphorodihalidates to be used and the monoamine compound to be used.
In the monoamine compound used in the present invention, the monoamine compound having one primary amino group and / or secondary amino group in the molecule may be either an aromatic monoamine compound or an aliphatic monoamine compound, The diamine compound having two primary amino groups and / or secondary amino groups in the molecule may be either an aromatic diamine compound or an aliphatic diamine compound.
In the present invention, the aromatic monoamine compound is preferably a compound represented by the general formula (IIa)
(Wherein, Ar 1 represents an aryl group, Y 1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an arylalkyl group, when Y 1 aryl date, Y 1 is may be the same as Ar 1 , Or may be different).
When the aryl groups Ar 1 and Y 1 are aryl groups, the aryl groups Ar 1 and Y 1 are preferably aryl groups having 6 to 12 carbon atoms. These aryl groups may have substituent An alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, or a substituent which is inert to the reaction as described above. Accordingly, examples of such aryl groups include phenyl, tolyl, xylanyl, trimethylphenyl, methoxyphenyl, naphthyl, methylnaphthyl, biphenylyl and methylbiphenyl groups.
When Y 1 is an alkyl group, such an alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 6 carbon atoms, and the number of carbon atoms is 3 The above alkyl groups may be linear or branched and may be branched. Examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and dodecyl. The alkyl group may have a heterocyclic group which is inert to the reaction as described above as a substituent.
When Y 1 is an alkenyl group, such an alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms such as an allyl group or an isopropenyl group. The alkenyl group may have a heterocyclic group that is inert to the reaction as described above as a substituent.
When Y < 1 > is a cycloalkyl group, such a cycloalkyl group may have, on the carbon atom forming the ring, an alkyl group having 1 to 6 carbon atoms or a total of carbon atoms which may have a substituent Is a cycloalkyl group having a number of 5 to 20, preferably 5 to 12, and therefore specific examples of such cycloalkyl groups include cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethyl Cyclohexyl, ethylcyclohexyl, and the like.
When Y 1 is an arylalkyl group, examples of the arylalkyl group include a benzyl group and phenylethyl. The arylalkyl group may also have an alkyl group of 1 to 6 carbon atoms on the aromatic ring or a substituent which is inert to the reaction as described above.
Thus, in the present invention, preferred examples of the aromatic monoamine compound include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3- Naphthylamine, 2-naphthylamine, 2-biphenylyl amine, 3-biphenylyl amine, 4-biphenylyl amine, Phenyl aniline, N-methylaniline, N-ethyl aniline, aminopyridines and the like.
In the present invention, the aromatic diamine compound is preferably a compound represented by the general formula (IIb)
(Wherein, Ar 2 represents a divalent group containing an aromatic ring, each of which in combination with the two nitrogen atoms in the molecule, Y 2 and Y 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group Or an arylalkyl group, and Y 2 and Y 3 may be the same or different).
As described above, in the present invention, the divalent Ar 2 having an aromatic ring is bonded to two nitrogen atoms in a molecule forming a diamine compound, and the aromatic ring has an alkyl group having 1 to 6 carbon atoms Or may have a substituent which is inert to the reaction as described above.
Therefore, a preferred one of the divalent Ar 2 having such an aromatic ring is an arylene group, and as a preferable example thereof, an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted o -Phenylene, m-phenylene, p-phenylene, naphthylene, biphenylene group and the like.
In the present invention, as a separate one of divalent Ar 2 having a preferable aromatic ring,
(Wherein Z represents a divalent group selected from an alkylene group, a cycloalkylene group, an oxygen atom, a sulfur atom, a disulfide group, a sulfoxide group, a sulfonyl group and a carbonyl group) .
In the present invention, among these arylene groups of divalent Ar 2 , those in which the divalent Z is, for example, an alkylene group or an oxygen atom are particularly preferably used.
2 When the top Z is an alkylene group, the alkylene group may have an aryl group such as a phenyl group as a substituent. 2 When Z is an alkylene group, such alkylene groups preferably have a number of carbon atoms in the range of 1 to 6, and examples thereof include methylene, ethylene, ethylidene, dimethylmethylidene, methylethylmethylidene group and the like For example. Examples of the alkylene group having a phenyl group as a substituent include phenylmethylidene, diphenylmethylidene, and the like.
2 When Z is a cycloalkylene group, examples of the cyclohexylene group or the cyclohexylidene group, which may have an alkyl group having 1 to 6 carbon atoms or a substituent inert to the reaction as described above on the carbon atom forming the ring, .
Y 2 and Y 3 may each independently be the same as or different from Y 1, and may be independently the same as the aryl group Ar 1 . Therefore, Y 2 and Y 3 may be the same or different.
Therefore, in the present invention, preferred examples of the aromatic diamine compound include aromatic diamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene and 2,6-diaminotoluene Diaminobiphenyls such as 4,4'-diaminobiphenyl, bis (4-aminophenyl) methane, 1,1-bis (4-aminophenyl) (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 1,1-bis -Bis (4-aminophenyl) butane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, and diaminopyridines.
In the present invention, the aliphatic monoamine compound is preferably a compound represented by the general formula (IVa)
(Wherein, Ay 1 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, Y 4 is by a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, or Ay 1 and Y 4 are Co, 5 In this case, the ring may contain an oxygen atom and / or a nitrogen atom as an atom forming the ring. When the atom forming the ring is a nitrogen atom, the nitrogen atom may be substituted with an oxygen atom and / And does not have a hydrogen atom bonded thereto).
When the aforementioned Ay 1 is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 6, The alkyl group may be linear or branched, and examples of such an alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl and dodecyl. The alkyl group may have a heterocyclic group which is inert to the reaction as described above as a substituent.
When Ay 1 is an alkenyl group, such an alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms such as an allyl group or an isopropenyl group. The alkenyl group may have a heterocyclic group which is inert to the above-mentioned reaction as a substituent.
When Ay 1 is a cycloalkyl group, such a cycloalkyl group may have on the carbon atom forming the ring an alkyl group having 1 to 6 carbon atoms or a total carbon atom which may have a substituent which is inert to the reaction as described above Is a cycloalkyl group having a number of 5 to 20, preferably 5 to 12, and therefore specific examples of such cycloalkyl groups include cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethyl Cyclohexyl, ethylcyclohexyl, and the like.
When Ay 1 is an arylalkyl group, examples of the arylalkyl group include a benzyl group and a phenylethyl group.
Therefore, in the present invention, examples of the aliphatic monoamine compound include aliphatic monoamine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, hexylamine, Diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-n-butylamine, (2-ethylhexyl) amine, dicyclohexylamine, dibenzylamine, allylamine, morpholine, diallylamine, 1-aminoethyl- Piperazines such as piperazine, piperazine, piperazine and piperazine, and mixtures of any two or more thereof.
In the present invention, the aliphatic diamine compound is preferably a compound represented by the general formula (IVb)
(Wherein Ay 2 represents an alkylene group or a cycloalkylene group which may have an aromatic group on the carbon atom or between carbon atoms, Y 5 and Y 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, Or Ay 2 and Y 5 may jointly form a 5-membered to 7-membered ring, or Ay 2 and Y 6 may jointly form a 5-membered to 7-membered ring, or Ay 2 and Y 5 may form a 5- And Y < 6 > may be taken together to form a 5-membered to 7-membered ring).
When the group Ay 2 is an alkylene group, the alkylene group may have an aryl group such as a phenyl group as a substituent. When the group Ay 2 is an alkylene group, such an alkylene group preferably has a carbon number of 1 to 6, and examples thereof include methylene, ethylidene, dimethylmethylidene, methylethylmethylidene group, etc. . Examples of the alkylene group having a phenyl group as a substituent include phenylmethylidene, diphenylmethylidene, 1-phenylethylene and 1,2-diphenylethylene groups.
When the group Ay 2 is a cycloalkylene group, such a cycloalkylene group may be an alkyl group having 1 to 6 carbon atoms on the carbon atom forming the ring or a cycloalkyl group which may have a substituent which is inert to the reaction as described above A hexylene group or a cyclohexylidene group.
When the group Ay 2 is an arylalkyl group, examples of the arylalkyl group include a benzyl group and a phenylethyl group.
The alkylene group which may have an aromatic group between the carbon atoms is preferably a group represented by the general formula (V)
(Wherein Y represents an arylene group which may have a substituent which is inert to the reaction on the aromatic ring as described above, and A 1 and A 2 each independently represent an alkylene group having 1 to 6 carbon atoms.) Quot;
In the divalent group represented by the general formula (V), the arylene group is, for example, a phenylene group, a naphthylene group or a biphenylene group, preferably a phenylene group, , And the number of carbon atoms is 1 to 4. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
Therefore, as a preferable specific example of the divalent group represented by the general formula (V), for example, the following can be mentioned.
Therefore, in the present invention, examples of the aliphatic diamine compound include aliphatic diamines such as ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, (Aminomethyl) cyclohexane, 1,3-bis (2,2'-aminoethyl) benzene, 1,4-bis 3-bis (aminomethyl) benzene, 2-methyl-4-imidazoline and the like.
According to the present invention, as described above, the phosphomonalohalidate is used as a phosphorus monohydrate by the dehydrohalogenation reaction, that is, condensation reaction with at least one amine compound selected from a monoamine compound and a diamine compound, The intended phosphoric acid ester amide can be obtained in accordance with the amine and the amine compound to be used.
Further, according to the present invention, as described above, phosphorodihalidate is used as a phosphohalidate, and this is subjected to a dehydrohalogenation reaction with a monoamine compound, that is, a condensation reaction, Corresponding to the monoamine compound to be used and the monoamine compound to be used, a desired phosphoric acid ester amide can be obtained.
In the reaction of these phosphorohalidates with amine compounds, according to the present invention, 0.5 equivalents or more, preferably 0.8 equivalents to 1.2 equivalents of the amine compound are added to the phosphorous halide at a temperature of 130 占 폚 or higher , The corresponding phosphoric acid ester amides can be obtained in a high yield relative to the amine compound.
In the present invention, one equivalent of phosphorodihalidates is a value obtained by dividing one mole of the phosphohalidate by the number of halogen atoms of the phosphorohalidate, and one equivalent of the amine compound is And the molar amount of the amine compound divided by the number of the primary and secondary amino groups of the amine compound.
Thus, for example, one equivalent of diphenylphosphorochloridate is 1 mole equivalent thereof, and one equivalent of phenylphosphorodichloridate is 0.5 mole equivalent thereof. Since aniline has one primary amino group and piperidine has one secondary amino group, one equivalent of the aniline is one mole thereof. Since phenylenediamine and piperazine each have two primary amino groups and secondary amino groups in the molecule, one equivalent thereof is 0.5 mole of all thereof.
In the process of the present invention, the reaction solvent is not necessarily used in the reaction of the phosphorohalidates and the amine compound, but the reaction solvent is preferably used so that the reaction proceeds smoothly and post- A reaction solvent having a boiling point of 130 ° C or higher is used. When the reaction solvent is used, the lower limit of the reaction solvent is not particularly limited, but is generally 0.5 parts by weight or more, and preferably 1 part by weight or more, relative to 1 part by weight of the phosphohalidate used. On the other hand, the upper limit of the amount of the reaction solvent to be used is generally 5 parts by weight or less, preferably 2 parts by weight or less, based on 1 part by weight of the phosphorohalidate used, from the viewpoint of volume efficiency.
According to the present invention, the above-mentioned proportion of phosphorohalidates and amine compounds are usually reacted at room temperature or, if necessary, at a temperature somewhat up to about 50 ° C, preferably with a reaction solvent, The reaction is initiated and then reacted at a temperature of at least 130 캜, preferably at the reflux temperature of the reaction solvent used.
In the present invention, the reaction is carried out at a temperature of 130 ° C or higher, that is, a step of reacting at a temperature of 130 ° C or higher in the reaction of the phosphorohalidate and the amine compound in the above- .
Although not limiting to the method of the present invention, a preferred embodiment of the process of the present invention is a process wherein the amine compound and the reaction solvent are introduced into the reaction vessel at room temperature or, if necessary, The amine compound is dissolved in the reaction solvent, and then the phosphorous halide is gradually added to the amine compound solution while stirring the obtained amine compound solution. Thus, during the addition of the phosphorous halide to the amine compound solution slowly, phosphoric acid ester amides of the desired phosphoric acid and hydrogen halide of the amine compound are precipitated from the amine compound solution, and the reaction mixture is composed of phosphoric acid ester amides and amine To form a dispersion comprising the hydrohalide salt of the compound.
Subsequently, when the phosphorohalidate is added all at once, the temperature of the reaction mixture is gradually raised to the initial reaction temperature, that is, to 130 ° C or higher, preferably to the reflux temperature of the used reaction solvent, and the temperature is maintained for 30 minutes The reaction is continued for several hours to several hours. Thus, while the reaction mixture is heated to the initial reaction temperature, depending on the type of amine compound and phosphorohalidate used, the reaction mixture is usually heated to about 100 ° C to 120 ° C The phosphoric acid ester amides are dissolved in the reaction solvent to form a dispersion in which only the hydrogen halide salt of the amine compound is precipitated.
Thereafter, when the reaction mixture is heated to the initial reaction temperature, that is, to a temperature of 130 ° C or higher, preferably to the reflux temperature of the used reaction solvent, the halogenation of the amine compound which is not dissolved in the reaction solvent The solids of the hydrogencarbonate gradually decrease with the progress of the reaction from about the time when the temperature of the reaction mixture reaches about 130 DEG C, and at the end of the reaction at the desired reaction temperature, the hydrohalide salt of the amine compound is completely eliminated, The reaction mixture becomes a uniform and transparent solution. Thus, when the reaction mixture becomes a uniform and transparent solution, the reaction is terminated.
Therefore, in the present invention, as described above, the phosphoric acid ester amide is dissolved in the reaction solvent to obtain a dispersion liquid in which only the hydrogen halide salt of the amine compound precipitates, and then the desired reaction temperature, that is, , It is preferable to continue the reaction until all of the hydrogen halide salt of the amine compound disappears at the reflux temperature of the reaction solvent used and the reaction mixture forms a uniform and transparent solution, that is, the reaction is terminated . Thus, at a temperature of 130 占 폚 or higher, preferably at the reflux temperature of the reaction solvent used, all of the hydrogen halide salt of the amine compound is completely eliminated until the reaction mixture forms a uniform and transparent solution, Is usually in the range of 30 minutes to several hours, although it depends on the kind of the amine compound and phosphorous halide used.
In the present invention, the mode of reacting the amine compound with the phosphohalidate is not limited to the above example. For example, if necessary, the amine compound is dissolved in a reaction solvent and heated to about 100 ° C to about 130 ° C On the other hand, phospholor halide may likewise be dissolved in a reaction solvent, heated to about 100 ° C to about 130 ° C, and then added with a solution of phosphorol halide to a solution of the amine compound.
As described later, according to the present invention, it is preferable that an inert gas or air flow in the reaction vessel throughout the reaction to remove the generated hydrogen halide gas outside the reaction system.
In the present invention, the upper limit of the reaction temperature is usually 250 占 폚 or lower, preferably 240 占 폚 or lower, although it depends on the reaction solvent when a reaction solvent is used. Particularly, in the present invention, when a reaction solvent is used, the reaction temperature is preferably in the range of 140 to 220 캜 for practical reasons, although it depends on the reaction solvent.
Examples of the reaction solvent having a boiling point of 130 ° C or higher include aromatic hydrocarbon solvents such as xylene, mesitylene, cumene, pseudocumene, solvent naphtha and so-called naphtha solvents, aliphatic hydrocarbon solvents such as isoparaffin solvents, Halogenated aromatic hydrocarbon solvents such as benzene, dichlorobenzene and trichlorobenzene, aromatic ether solvents such as diphenyl ether, and mixtures thereof are preferably used.
In the present invention, an organic solvent containing various aromatic hydrocarbons as a main component and referred to as a solvent naphtha or naphtha solvent and having a boiling point of 130 ° C or higher is contained in the above aromatic hydrocarbon solvent, and an isoparaffinic hydrocarbon is used as a main component , And an organic solvent having a boiling point of 130 ° C or higher is included in the aliphatic hydrocarbon solvent.
According to the method for producing phosphoric acid ester amides according to the present invention, an excess of amine compound is not used relative to 1 equivalent of phosphorohalidate, and according to a preferred embodiment, 0.8 equivalents to 1.2 equivalents, more preferably, By using 1 equivalent, the intended phosphoric acid ester amide can be obtained at a high yield relative to the amine compound. The reason is as follows.
That is, when the amine compound is used in an amount of 1 equivalent of the amine compound and 1 equivalent of the phosphorohalidate, the amine compound acts both as a reactant and as a hydrogen halide capturing agent to promote the reaction. Therefore, one equivalent of the amine compound and phosphorous halide 0.5 equivalents of an amine compound and 0.5 equivalents of phosphorohalidate in one equivalent of a date are reacted even at a relatively low temperature to produce corresponding phosphate ester amides. However, in this case, since 0.5 equivalent of the remaining amine compound captures the hydrogen halide produced by the above reaction to form the hydrohalide salt, in the state of the hydrohalide salt, 0.5 equivalents of the remaining phosphorohalidate Lt; / RTI > Thus, by further increasing the reaction temperature, the hydrogen halide gas is released from the hydrogen halide salt of the amine compound and is removed from the reaction system, and the amine compound is returned to the free amine compound again. Therefore, And reacts. The hydrogen halide generated at this time is removed from the reaction system without being trapped in the amine compound under high temperature reaction conditions or captured by the amine compound and hydrogen halide gas is likewise removed from the hydrogen halide salt under high temperature reaction conditions And is removed from the reaction system.
Therefore, in the production of phosphoric acid ester amides according to the present invention, it is necessary that the reaction system is in communication with the outside of the reaction system so that the hydrogen halide gas produced by the condensation reaction of the phosphorohalidates and the amine compound is removed from the reaction system In particular, according to the present invention, it is preferable to forcibly remove the hydrogen halide gas which has been separated from the hydrogen halide salt of the amine compound, out of the reaction system, thereby promoting the smooth progress of the reaction.
Therefore, according to the present invention, in the reaction of the phosphorohalidates and the amine compound, an inert gas such as nitrogen, helium, argon, carbon dioxide gas or the like is blown into the reaction vessel, It is preferable to carry out the reaction under an air stream or the reaction under suction and decompression.
In order to isolate the desired phosphoric acid ester amides from the resulting reaction mixture after reacting the phosphorohalidates and the amine compound in this way, for example, the obtained reaction mixture is cooled to precipitate the reaction product, And then washed with an aqueous base solution such as hydrochloric acid, an aqueous base solution such as sodium carbonate and then with warm water to remove unreacted materials and then dried to obtain desired phosphoric acid ester amides. Thereafter, if necessary, it may be washed with a lower alcohol such as methanol or ethanol or acetone, or recrystallized from a thermal alcohol.
According to the present invention, desired phosphoric acid ester amides can be thus obtained in correspondence with the phosphorodihalidates and amine compounds.
That is, the phosphoramido halide represented by the general formula (Ia) is reacted with the aromatic monoamine compound represented by the general formula (IIa) to obtain the phosphoric acid ester amide represented by the general formula (VIa) , And the phosphoramonohalide represented by the general formula (Ia) is reacted with the aromatic diamine compound represented by the general formula (IIb) to obtain the phosphoric acid ester amide represented by the general formula (VIb) .
Likewise, the phosphoramido halide represented by the general formula (Ia) is reacted with the aliphatic monoamine compound represented by the general formula (IVa) to obtain the phosphoric acid ester amide represented by the general formula (VIIa) (VIIb) can be obtained by reacting the phosphorammonohalidate represented by the above general formula (Ia) with the aliphatic diamine compound represented by the general formula (IVb), to obtain a phosphoric acid ester amide represented by the general formula .
Further, the phosphorodihalidate represented by the above general formula (Ib) is reacted with the aromatic monoamine compound represented by the general formula (IIa) to obtain the phosphoric acid ester amide represented by the general formula (VIIIa) Similarly, the phosphorodihalidates represented by the above general formula (Ib) are reacted with the aliphatic monoamine compound represented by the general formula (IVa) to obtain phosphoric acid ester amides represented by the general formula (VIIIb) Can be obtained.
Accordingly, in the present invention, the phosphoric acid ester amides represented by the general formula (VIa) include, for example, the following.
Examples of the phosphate ester amides represented by the general formula (VIb) include the following.
The phosphate ester amides represented by the general formula (VIIa) include, for example, the following.
The phosphate ester amides represented by the general formula (VIIb) include, for example, the following.
The phosphate ester amides represented by the general formula (VIIIa) include, for example, the following.
The phosphate ester amides represented by the general formula (VIIIb) include, for example, the following.
Example
Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples at all. Hereinafter, the melting point is a value obtained from the peak appearing first when the temperature is raised at 20 캜 / min in the differential thermal-thermal weight measurement.
Example 1
9.8 g (0.105 mol) of aniline and 35 mL of mesitylene were injected into a round bottom flask at room temperature, and the aniline was dissolved in mesitylene. While stirring the obtained solution, 26.9 g (0.100 mol) of diphenylphosphorochloridate was slowly added dropwise to the solution at 40 ° C or lower over 10 minutes. At this time, anilino diphenylphosphate and aniline hydrochloride were precipitated from the solution, and the reaction mixture became a dispersion containing the precipitate.
After completion of the dropwise addition, the reaction mixture was gradually heated to 170 to 180 DEG C over 30 minutes, and mesitylene was refluxed and reacted at the same temperature for 1 hour. When the temperature of the reaction mixture exceeded 100 캜, anilinodiphenyl phosphate was dissolved in mesitylene, resulting in a dispersion in which only aniline hydrochloride was precipitated. At the beginning of the reaction, the solids of the aniline hydrochloride which was not dissolved in mesitylene gradually decreased with the progress of the reaction when the temperature of the reaction mixture reached 130 ° C or higher. At the end of the reaction, the solids of the aniline hydrochloride disappeared, and the reaction mixture became a uniform and transparent solution.
During the reaction, nitrogen gas was caused to flow in a round bottom flask, and 3.0 g of the generated hydrogen chloride gas was recovered. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain a precipitate.
The precipitate was subjected to suction filtration, washed with a dilute hydrochloric acid aqueous solution, a saturated sodium carbonate aqueous solution and a hot water in this order, and then dried to obtain 27.8 g of anilino diphenyl phosphate. The yield for aniline was 81.5%. A melting point of 131.5 DEG C (melting point 130 DEG C described in Japanese Patent Application Laid-Open No. 49-72346).
Example 2
In the same manner as in Example 1 except that 11.2 g (0.120 mol) of aniline was used, 30.5 g of anilino diphenyl phosphate was obtained. The yield for aniline was 78.2%. Melting point 132.0 占 폚.
Example 3
Anilinodiphenyl phosphate (29.5 g) was obtained in the same manner as in Example 1, except that 9.30 g (0.100 mol) of aniline and 33.6 g (0.125 mol) of diphenylphosphorochloridate were used. The yield for diphenylphosphorochloridate was 72.6%. Melting point 131.2 ° C.
Example 4
Except that 11.3 g (0.122 mol) of aniline, 23.7 g (0.088 mol) of diphenylphosphorochloridate and 2.9 g (0.014 mol) of phenylphosphorodichloridate were used in the same manner as in Example 1, 30.1 g of a mixture of anilinodiphenylphosphate and dianilinophenylphosphate was obtained. As a result of analysis by liquid chromatography, the content of monoanilide in the mixture was 86.6% by weight. The yield of the mixture for aniline was 75.9%. Melting point 130.8 ° C.
Example 5
Except that 32.5 g (0.100 mol) of di (2,6-xylylene) phosphorochloridate was used in place of diphenylphosphorochloridate in Example 1, anilino di ( 2,6-xylenyl) phosphate (32.4 g). The yield for aniline was 81.0%. Melting point 127.2 ° C.
Example 6
Except that an isoparaffin-based solvent (isopar L manufactured by Exxon Mobil Chemical) was used as a solvent in place of mesitylene and the temperature of the reaction mixture at the time of the reaction was changed from 190 ° C to 200 ° C In the same manner, 29.2 g of anilino diphenyl phosphate was obtained. The yield for aniline was 85.6%. Melting point 133.2 ° C.
Example 7
26.4 g of anilino diphenyl phosphate was obtained in the same manner as in Example 1 except that diphenyl ether was used as a solvent instead of mesitylene and the temperature of the reaction mixture in the reaction was changed to 200 to 220 캜 . The yield for aniline was 77.4%. Melting point 130.8 ° C.
Example 8
Except that xylene was used as a solvent in place of mesitylene and the temperature of the reaction mixture at the time of the reaction was changed from 140 ° C to 145 ° C and the reaction time was changed to 2 hours, 25.7 g of diphenyl phosphate was obtained. The yield for aniline was 75.3%. Melting point 130.9 ° C.
Example 9
23.9 g of morpholinodiphenyl phosphate was obtained in the same manner as in Example 1, except that 9.1 g (0.105 mol) of morpholine was used instead of aniline. The yield for morpholine was 71.4%. A melting point of 76.1 DEG C (melting point 71 DEG C described in Japanese Patent Application Laid-Open No. 2000-154277).
Example 10
4.5 g (0.052 mol) of piperazine was used in place of aniline in Example 1, and the same isoparaffin as above was used instead of mesitylene, and the temperature of the reaction mixture at the time of the reaction was adjusted to 190 to 200 C, 18.5 g of 1,4-piperazinyl bis (diphenylphosphate) was obtained in the same manner. The yield for piperazine was 64.3%. Melting point 184 占 폚 (melting point 184 占 폚 described in Japanese Patent Laid-Open Publication No. 2000-327834).
Example 11
21.6 g of 1,3-bis (diphenylphosphoronamino) benzene was obtained in the same manner as in Example 1, except that 5.7 g (0.053 mol) of m-phenylenediamine was used instead of aniline. The yield for m-phenylenediamine was 71.5%. (Melting point 183 DEG C to 184 DEG C described in J. Chem. Soc. (C), 1971).
Example 12
(Ipzole) 150 (manufactured by Idemitsu Kosan Co., Ltd.) was used instead of mesitylene in place of aniline by using 5.7 g (0.053 mole) of p-phenylenediamine in place of aniline in Example 1 , 22.9 g of 1,4-bis (diphenylphosphoronamino) benzene was obtained in the same manner as in Example 1, except that the temperature of the reaction mixture at the time of the reaction was 200 ° C and the reaction time was 4 hours. The yield for p-phenylenediamine was 75.9%. (Melting point 210 to 211 C described in J. Chem. Soc. (C), 1971).
Example 13
Except that 10.4 g (0.053 mol) of 4,4'-diaminodiphenylmethane was used in place of p-phenylenediamine and the reaction time was changed to 5 hours in Example 12, 30.8 g of 4'-bis (diphenylphosphorylamidophenyl) methane was obtained. The yield based on 4,4'-diaminodiphenylmethane was 88.6%. A melting point of 186.5 DEG C (melting point 194 DEG C described in Japanese Patent Laid-Open No. 2003-238580).
Comparative Example 1
30.0 g (0.323 mol) of aniline and 45 mL of toluene were introduced into a round bottom flask, and 40.8 g (0.152 mol) of diphenylphosphorochloridate was slowly added dropwise to the mixture while stirring at room temperature. After completion of the dropwise addition, the temperature of the reaction mixture was adjusted to 80 캜 and stirring was continued for 1 hour, followed by cooling to obtain a precipitate. This precipitate was filtered out, washed with water and dried to obtain 45.1 g of anilino diphenyl phosphate. The yield for aniline was 43.0%. Melting point 131.6 ° C.
Comparative Example 2
In the same manner as in Example 1 except that diphenylphosphorochloridate was added dropwise at room temperature and the reaction mixture was allowed to react at room temperature for 1 hour without heating the reaction mixture, anilinodiphenylphosphate 13.4 g. The yield for aniline was 39.3%. Melting point 131.1 캜.
Claims (14)
≪ RTI ID = 0.0 > phosphomonohalides < / RTI >
In general formula (Ib)
Phosphododihalidates < RTI ID = 0.0 >
(Wherein R 1 , R 2 and R 3 are each independently an alkyl, cycloalkyl, aryl or arylalkyl group which may have a substituent which is inactive in the reaction, And X represents a halogen atom,
At least one amine compound selected from a monoamine compound having one primary amino group and / or secondary amino group in the molecule and a diamine compound having two primary amino groups and / or secondary amino groups in the molecule and Dehydrohalogenation reaction, or
(B) a phospholodihalidate as the phosphohaloylidate is dehydrohalogenated with a monoamine compound having one primary amino group and / or secondary amino group in the molecule, In the process for producing a phosphoric acid ester amide,
Reacting the phosphorohalidate with the amine compound at a temperature of at least < RTI ID = 0.0 > 130 C. < / RTI >
(Wherein, Ar 1 represents an aryl group, Y 1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an arylalkyl group, when Y 1 aryl date, Y 1 is may be the same as Ar 1 (VIa) may be reacted with an aromatic monoamine compound represented by the general formula (VIa)
Lt; RTI ID = 0.0 > (II) < / RTI >
(Wherein, Ar 2 represents a divalent group containing an aromatic ring, each of which in combination with the two nitrogen atoms in the molecule, Y 2 and Y 3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group Or an arylalkyl group, and Y 2 and Y 3 may be the same or different) to react with an aromatic diamine compound represented by the general formula (VIb)
Lt; RTI ID = 0.0 > (II) < / RTI >
(Wherein, Ay 1 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, Y 4 is by a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, or Ay 1 and Y 4 are Co, 5 In this case, the ring may contain an oxygen atom and / or a nitrogen atom as an atom forming the ring. When the atom forming the ring is a nitrogen atom, the nitrogen atom may be substituted with an oxygen atom and / (VIIa) is reacted with an aliphatic monoamine compound represented by the general formula (VIIa)
Lt; RTI ID = 0.0 > (II) < / RTI >
(Wherein Ay 2 represents an alkylene group or a cycloalkylene group which may have an aromatic group on the carbon atom or between carbon atoms, Y 5 and Y 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, Or Ay 2 and Y 5 may jointly form a 5-membered to 7-membered ring, or Ay 2 and Y 6 may jointly form a 5-membered to 7-membered ring, or Ay 2 and Y 5 may form a 5- And Y < 6 > may form a 5-membered to 7-membered ring together with the aliphatic diamine compound represented by the general formula (VIIb)
Lt; RTI ID = 0.0 > (II) < / RTI >
(Wherein, Ar 1 represents an aryl group, Y 1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an arylalkyl group, when Y 1 aryl date, Y 1 is may be the same as Ar 1 (VIIIa) may be reacted with an aromatic monoamine compound represented by the general formula (VIIIa)
Lt; RTI ID = 0.0 > (II) < / RTI >
(Wherein, Ay 1 represents an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, Y 4 is by a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or an arylalkyl group, or Ay 1 and Y 4 are Co, 5 In this case, the ring may contain an oxygen atom and / or a nitrogen atom as an atom forming the ring. When the atom forming the ring is a nitrogen atom, the nitrogen atom may be substituted with an oxygen atom and / (VIIIb) is reacted with an aliphatic monoamine compound represented by the general formula
Lt; RTI ID = 0.0 > (II) < / RTI >
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| JP2000154277A (en) | 1998-09-18 | 2000-06-06 | Shikoku Chem Corp | Flame-retardant resin composition |
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| JPH10175985A (en) | 1996-12-17 | 1998-06-30 | Tosoh Corp | Nitrogen-containing organic phosphoric acid compound and flame-retardant resin composition compounding the same |
| JP2000154277A (en) | 1998-09-18 | 2000-06-06 | Shikoku Chem Corp | Flame-retardant resin composition |
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