CN104395329B - The manufacture method of phosphoric ester amides class - Google Patents
The manufacture method of phosphoric ester amides class Download PDFInfo
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- CN104395329B CN104395329B CN201380032297.3A CN201380032297A CN104395329B CN 104395329 B CN104395329 B CN 104395329B CN 201380032297 A CN201380032297 A CN 201380032297A CN 104395329 B CN104395329 B CN 104395329B
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- -1 ester amides Chemical class 0.000 title claims abstract description 167
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 150000001412 amines Chemical class 0.000 claims abstract description 72
- 239000002253 acid Substances 0.000 claims abstract description 66
- 150000002148 esters Chemical class 0.000 claims abstract description 53
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 15
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 15
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 105
- 125000003118 aryl group Chemical group 0.000 claims description 58
- 125000000217 alkyl group Chemical group 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 34
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 32
- 125000003342 alkenyl group Chemical group 0.000 claims description 29
- 238000006467 substitution reaction Methods 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 125000001118 alkylidene group Chemical group 0.000 claims description 23
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 18
- 150000001721 carbon Chemical group 0.000 claims description 14
- 125000004429 atom Chemical group 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000004430 oxygen atom Chemical group O* 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
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 70
- 239000002585 base Substances 0.000 description 42
- 239000000203 mixture Substances 0.000 description 31
- 239000000376 reactant Substances 0.000 description 25
- 239000004305 biphenyl Substances 0.000 description 20
- 235000010290 biphenyl Nutrition 0.000 description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- 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 15
- 229910052736 halogen Inorganic materials 0.000 description 14
- 150000002367 halogens Chemical group 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- WVPKAWVFTPWPDB-UHFFFAOYSA-M dichlorophosphinate Chemical compound [O-]P(Cl)(Cl)=O WVPKAWVFTPWPDB-UHFFFAOYSA-M 0.000 description 10
- 0 CC1=CC(*C2)C2=C1 Chemical compound CC1=CC(*C2)C2=C1 0.000 description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 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
- 239000007788 liquid Substances 0.000 description 6
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 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
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 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
- 125000001309 chloro group Chemical group Cl* 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
- WVPKAWVFTPWPDB-UHFFFAOYSA-N dichlorophosphinic acid Chemical class OP(Cl)(Cl)=O WVPKAWVFTPWPDB-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
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([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
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 125000000286 phenylethyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000005023 xylyl group Chemical group 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
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 2
- 125000005810 2,5-xylyl group Chemical group [H]C1=C([H])C(=C(*)C([H])=C1C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- BYMMIQCVDHHYGG-UHFFFAOYSA-N Cl.OP(O)(O)=O Chemical compound Cl.OP(O)(O)=O BYMMIQCVDHHYGG-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 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
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 125000004956 cyclohexylene group Chemical group 0.000 description 2
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 2
- 238000002386 leaching Methods 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
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MFFNRVNPBJQZFO-UHFFFAOYSA-N (2,6-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(O)=O MFFNRVNPBJQZFO-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical class C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical class CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 150000005003 1-naphthylamines Chemical class 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
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical class CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 1
- 150000005000 2,6-diaminotoluenes Chemical class 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical class CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- PGCRDIRKSWIOPB-UHFFFAOYSA-N 2-methyl-2,3-dihydro-1h-imidazole Chemical class CC1NC=CN1 PGCRDIRKSWIOPB-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 150000005004 2-naphthylamines Chemical class 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical class CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-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
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CEMPQTAVSQXWDU-KPGFUFOFSA-N C/C=C\C(\OP(Nc1ccccc1)(Oc1ccccc1)=O)=C/C Chemical compound C/C=C\C(\OP(Nc1ccccc1)(Oc1ccccc1)=O)=C/C CEMPQTAVSQXWDU-KPGFUFOFSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- RHZGBLUHBKWHJH-UHFFFAOYSA-N NC1=CC=CC=C1.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound NC1=CC=CC=C1.C1(=CC=CC=C1)PC1=CC=CC=C1 RHZGBLUHBKWHJH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003927 aminopyridines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical class NCCCCCN VHRGRCVQAFMJIZ-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
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-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
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction 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
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- PXSXRABJBXYMFT-UHFFFAOYSA-N n-hexylhexan-1-amine Chemical compound CCCCCCNCCCCCC PXSXRABJBXYMFT-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-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
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BCIIMDOZSUCSEN-UHFFFAOYSA-N piperidin-4-amine Chemical class NC1CCNCC1 BCIIMDOZSUCSEN-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-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
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 125000003375 sulfoxide group Chemical group 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
- 150000003942 tert-butylamines Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005406 washing Methods 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
- C07F9/247—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
- C07F9/2458—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
- C07F9/2475—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
-
- 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, a kind of method for manufacturing phosphoric ester amides class is provided, during it makes molecule there is de-hydrogen halide in the amines with 1 or 2 primary amino radicals and/or secondary amino group with monohaloalkyl phosphoric acid ester, so as to manufacture the phosphoric ester amides class corresponding to above-mentioned monohaloalkyl phosphoric acid ester, wherein, include in the method：Reacted at a temperature of making above-mentioned monohaloalkyl phosphoric acid ester and above-mentioned amines more than 130 DEG C and without excessively using amines relative to halophosphoric acid esters.
Description
Technical field
The present invention relates to the novel manufacturing method of phosphoric ester amides class.
Background technology
Phosphoric ester amides class is used as fire retardant (for example, see specially in formed products, the fiber product for example in synthetic resin
Sharp document 1), its manufacture method is at present it is also known that several.
For example, generally can be by hexichol as the anilino- diphenyl phosphoester of a typical example of phosphoric ester amides class
Base phosphoryl chloride phosphorus oxychloride is obtained with the condensation reaction of aniline, i.e. dehydrochlorination reaction.
In the reaction, when diphenyl phosphoryl chloride and aniline respectively use 1 equivalent, the aniline of 0.5 equivalent and 0.5 equivalent
Diphenyl phosphoryl chloride reacts, and generates as the anilino- diphenyl phosphoester of target, but the aniline of remaining 0.5 equivalent is made
Form hydrochloride for hydrogen chloride capturing agent works, thus the diphenyl phosphoryl chloride unreacted of 0.5 equivalent and keep intact.
Therefore, manufactured during anilino- diphenyl phosphoester by the reaction of diphenyl phosphoryl chloride and aniline, it is generally relative
The aniline of 2 equivalents is used in the diphenyl phosphoryl chloride of 1 equivalent, wherein, make the diphenyl phosphoryl chloride of the aniline of 1 equivalent and 1 equivalent
React, the aniline of remaining 1 equivalent works as hydrogen chloride capturing agent, so as to realize diphenyl phosphoryl chloride in the reaction
Effective utilization (for example, see patent document 2).
But, in the manufacture of anilino- diphenyl phosphoester, like this, the diphenyl phosphoryl chloride relative to 1 equivalent makes
With the aniline of 2 equivalents, wherein, when the aniline of 1 equivalent is used as into hydrogen chloride capturing agent, the yield phase of anilino- diphenyl phosphoester
For aniline not over 50%, on the other hand, reaction neutralizes the operation that purifying anilinechloride carrys out aniline recovery after terminating
It is numerous and diverse, therefore, from from the perspective of aniline, what the above method was economically disadvantageous.
Thus, also carry out：The aliphatic of heteroaromatic amines, triethylamine using such as pyridine etc etc
Tertiary amine is used as hydrogen chloride capturing agent (for example, see patent document 3) instead of aniline.But, on these amine, aromatic series
Amine then more sometimes cannot be as hydrogen chloride capturing agent effectively function, in addition, in order to after the completion of reaction from their salt
Amine is reclaimed in hydrochlorate and is recycled, similarly need numerous and diverse operation.Also, according to such method, sometimes in gained
The stink that the amine by using is produced can be also remained in anilino- diphenyl phosphoester.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-193368 publications
Patent document 2：Japanese Unexamined Patent Publication 2000-154277 publications
Patent document 3：Japanese Unexamined Patent Publication 10-175985 publications
The content of the invention
Problems to be solved by the invention
The present invention is made for the above mentioned problem solved in the manufacture of conventional phosphoric ester amides class, and its purpose exists
In, there is provided a kind of novel manufacturing method of phosphoric ester amides class, the method can obtain mesh relative to amines with high yield
Mark phosphoric ester amides class and need not excessively use above-mentioned amines relative to phosphoryl chloride phosphorus oxychloride class.
Especially, it is an object of the present invention to provide a kind of novel manufacturing method of phosphoric ester amides class, the method is relative
Used using the amines of the scope more than 0.5 equivalent and less than 2.0, according to preferred mode in the phosphoryl chloride phosphorus oxychloride class of 1 equivalent
The amines of 0.8~1.2 equivalent, can obtain target phosphoric ester amides class relative to above-mentioned amines with high yield.
The scheme for solving problem
According to the present invention,
A kind of method for manufacturing phosphoric ester amides class is provided, it is characterised in that
(A) make selected from the monohaloalkyl phosphoric acid ester (phosphoro-monohalidates) and formula shown in formula (Ia)
(Ib) at least a kind halophosphoric acid esters in the dihalo phosphoric acid ester shown in selected from have in molecule 1 primary amino radical and/or
There is at least a kind amination in the diamine compound of 2 primary amino radicals and/or secondary amino group in the monoamine compound and molecule of secondary amino group
There is de-hydrogen halide in compound, or,
(B) make to have in above-mentioned dihalo phosphoric acid ester as halophosphoric acid esters and molecule 1 primary amino radical and/or secondary
There is de-hydrogen halide in the monoamine compound of amino,
So as to manufacture the phosphoric ester amides class corresponding to above-mentioned halophosphoric acid esters,
In the method, including：Sent out at a temperature of making above-mentioned halophosphoric acid esters and above-mentioned amines more than 130 DEG C
Raw reaction.
(in above-mentioned formula, R1、R2And R3Represent that it be in the reaction the alkane of inactive substitution base optionally to have independently of one another
Base, cycloalkyl, aryl or aryl alkyl, X represent halogen atom.)
According to the present invention, make the monohaloalkyl phosphoric acid ester shown in above-mentioned formula (Ia) that dehydrohalogenation occur with monoamine compound
During reaction, it is possible to use aromatic series monoamine compound or aliphatic monoamine compound.
According to the present invention, make the monohaloalkyl phosphoric acid ester shown in above-mentioned formula (Ia) that dehydrohalogenation occur with diamine compound
During reaction, it is possible to use aromatic diamine compound or aliphatic diamine compound.
In addition, according to the present invention, making the dihalo phosphoric acid ester shown in above-mentioned formula (Ib) occur with monoamine compound de-
When hydrogen halides reacts, it is possible to use aromatic series monoamine compound or aliphatic monoamine compound.
That is, according to the present invention, as preferred mode, there is provided following 6 methods.
(1) make monohaloalkyl phosphoric acid ester shown in aforementioned formula (Ia) with shown in the formula (IIa) as amines
Aromatic series monoamine compound reacts, so that the method for manufacturing the phosphoric ester amides class shown in formula (VIa).
(in formula, Ar1Represent aryl, Y1Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y1For
During aryl, Y1With Ar1Can be the same or different.)
(2) make monohaloalkyl phosphoric acid ester shown in aforementioned formula (Ia) with shown in the formula (IIb) as amines
Aromatic diamine compound reacts, so that the method for manufacturing the phosphoric ester amides class shown in formula (VIb).
(in formula, Ar2Represent respectively with molecule in 2 nitrogen atom bondings the divalent group comprising aromatic rings, Y2And Y3Respectively
From independently expression hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y2With Y3Can with it is identical can not also
Together.)
(3) the monohaloalkyl phosphoric acid ester shown in aforementioned formula (Ia) and the aliphatic monoamine chemical combination shown in formula (IVa) are made
Thing reacts, so that the method for manufacturing the phosphoric ester amides class shown in formula (VIIa).
(in formula, Ay1Represent alkyl, alkenyl, cycloalkyl or aryl alkyl, Y4Represent hydrogen atom, alkyl, alkenyl, ring
Alkyl or aryl alkyl, or, Ay1With Y45~7 yuan of rings can be collectively forming, now, above-mentioned ring can comprising oxygen atom and/or
Nitrogen-atoms is used as the atom for forming the ring.Wherein, when the atom for forming ring is nitrogen-atoms, the nitrogen-atoms is without bonded thereto
Hydrogen atom.)
(4) make monohaloalkyl phosphoric acid ester shown in aforementioned formula (Ia) with shown in the formula (IVb) as amines
Aliphatic diamine compound reacts, so that the method for manufacturing the phosphoric ester amides class shown in formula (VIIb).
(in formula, Ay2Represent alkylidene or ring alkylene with aromatic group optionally on carbon atom or between carbon atom
Base, Y5And Y6Hydrogen atom, alkyl, alkenyl, cycloalkyl or aryl alkyl are represented independently of one another, or, Ay2With Y5Can be total to
With 5~7 yuan of rings of formation, or Ay2With Y65~7 yuan of rings, or Ay can be collectively forming2With Y5With Y65~7 can be collectively forming
Yuan of rings.)
(5) make dihalo phosphoric acid ester shown in aforementioned formula (Ib) with shown in the formula (IIa) as amines
Aromatic series monoamine compound reacts, so that the method for manufacturing the phosphoric ester amides class shown in formula (VIIIa).
(in formula, Ar1Represent aryl, Y1Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y1For
During aryl, Y1With Ar1Can be the same or different.)
(6) make dihalo phosphoric acid ester shown in aforementioned formula (Ib) with shown in the formula (IVa) as amines
Aliphatic monoamine compound reacts, so that the method for manufacturing the phosphoric ester amides class shown in formula (VIIIb).
(in formula, Ay1Represent alkyl, alkenyl, cycloalkyl or aryl alkyl, Y4Represent hydrogen atom, alkyl, alkenyl, ring
Alkyl or aryl alkyl, or, Ay1With Y45~7 yuan of rings can be collectively forming, now, above-mentioned ring can comprising oxygen atom and/or
Nitrogen-atoms is used as the atom for forming the ring.Wherein, when the atom for forming ring is nitrogen-atoms, the nitrogen-atoms is without bonded thereto
Hydrogen atom.)
According to the present invention, in the methods described above, it is preferred that relative to the halophosphoric acid esters of 1 equivalent, 0.5 is set to work as
More than amount and less than 2 equivalents, especially the amines of 0.8~1.2 equivalent is reacted.
In addition, according to the present invention, in the methods described above, reaction dissolvent must not necessarily be used, but in order that reaction is suitable
Carry out sharply, preferably use reaction dissolvent, at this point it is possible to use the reaction dissolvent that boiling point is more than 130 DEG C.As such boiling
Point is more than 130 DEG C of reaction dissolvent, preferably uses aromatic hydrocarbon, halogenated aromatic hydrocarbon, fat selected from more than 130 DEG C of boiling point
At least a kind in race's hydrocarbon and aromatic series ethers.
The effect of invention
The method according to the invention, uses above-mentioned amines with only measuring, i.e. make by relative to halophosphoric acid esters
With more than 0.5 equivalent and less than 2 equivalents, preferably use 0.8~1.2 equivalent, can be relative to above-mentioned amines with high yield
Obtain target phosphoric ester amides class.
Specific embodiment
The manufacture method of phosphoric ester amides class of the invention is：(A) make selected from the monohaloalkyl phosphate shown in formula (Ia)
At least a kind halophosphoric acid esters in dihalo phosphoric acid ester shown in class and formula (Ib) with selected from having 1 primary in molecule
In diamine compound with 2 primary amino radicals and/or secondary amino group in the monoamine compound and molecule of amino and/or secondary amino group extremely
There is de-hydrogen halide in few a kind of amines, or,
(B) make to have in above-mentioned dihalo phosphoric acid ester as halophosphoric acid esters and molecule 1 primary amino radical and/or secondary
There is de-hydrogen halide in the monoamine compound of amino,
So as to manufacture the phosphoric ester amides class corresponding to above-mentioned halophosphoric acid esters,
In the method, including：Sent out at a temperature of making above-mentioned halophosphoric acid esters and above-mentioned amines more than 130 DEG C
Raw reaction.
(in above-mentioned formula, R1、R2And R3Represent that it be in the reaction the alkane of inactive substitution base optionally to have independently of one another
Base, cycloalkyl, aryl or aryl alkyl, X represent halogen atom.)
In the present invention, in the halophosphoric acid esters shown in above-mentioned formula (Ia) and (Ib), R1、R2And R3Table independently of one another
Show that optionally it is the inactive alkyl for replacing base, cycloalkyl, aryl or aryl alkyl to have to reaction, X represents halogen atom.
It is above-mentioned to replace base to refer to be not involved in halophosphoric acid esters of the invention and amine for inactive reaction in the present invention
The substitution base of the reaction of compound, such as except alkoxy, nitro, itrile group, the chlorine atom etc of methoxyl group etc can be included
Halogen atom outside, can also include the heterocyclic radical of the reaction for being not involved in halophosphoric acid esters of the invention and amines
Deng.It is same as below.
Abovementioned alkyl is preferably carbon number 1~20, more preferably 1~12, particularly preferred 1~6 alkyl, carbon number 3
More than alkyl can be that straight-chain can also be branched, as this alkyl, can for example include methyl, ethyl, propyl group,
Butyl, amyl group, hexyl, octyl group, nonyl, dodecyl etc..
Above-mentioned cycloalkyl be optionally formed ring carbon atom on have alkyl as substitution base total carbon atom number 5~
20th, preferably 5~12 cycloalkyl, as concrete example, can include cyclopenta, methylcyclopentyl, cyclohexyl, methylcyclohexyl,
Dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl etc..
In addition, above-mentioned aryl is preferably the aryl that carbon number is 6~12, and as substitution base optionally on aromatic rings
And there are one or more alkyl, the preferably alkyl of carbon number 1~6 and/or foregoing to reacting for inactive substitution
Base.Accordingly, as this aryl, can for example include phenyl, tolyl, xylyl, trimethylphenyl, methoxyphenyl,
Naphthyl, methyl naphthyl, xenyl, methyl biphenyl etc..
As aryl alkyl, for example, can include benzyl, phenethyl etc..Aryl alkyl also has carbon optionally on aromatic rings
The alkyl of atomicity 1~6, it is foregoing to reaction be inactive substitution base.
In addition, in above-mentioned halophosphoric acid esters, halogen atom X is chlorine atom, bromine atoms or iodine atom, preferably chlorine is former
Son.That is, in the present invention, above-mentioned halophosphoric acid esters are preferably phosphoryl chloride phosphorus oxychloride class.
Especially, in the present invention preferably, in the halophosphoric acid esters shown in aforementioned formula (Ia) and (Ib), R1、R2With
R3Be each independently optionally on aromatic rings the alkyl with carbon number 1~6, it is foregoing to reaction for inactive
Replace the aryl of base, particularly preferably phenyl, tolyl or xylyl, X is chlorine atom.
Therefore, in the present invention, as the preferred concrete example of the monohaloalkyl phosphoric acid ester shown in aforementioned formula (Ia), for example
Diphenyl phosphoryl chloride, two (tolyl) phosphoryl chloride phosphorus oxychlorides, two (p-methylphenyl) phosphoryl chloride phosphorus oxychlorides, two (2,6- xylyls) phosphorus can be included
It is double (xylyl) phosphoryl chloride phosphorus oxychlorides such as acyl chlorides, two (3,5- xylyls) phosphoryl chloride phosphorus oxychlorides, two (2,5- xylyls) phosphoryl chloride phosphorus oxychlorides, double (different
Propyl group phenyl) phosphoryl chloride phosphorus oxychloride, double (isobutyl phenenyl) phosphoryl chloride phosphorus oxychlorides, double (tert-butyl-phenyl) phosphoryl chloride phosphorus oxychlorides, two -1- naphthyls phosphoryl chloride phosphorus oxychlorides, two -
2- naphthyls phosphoryl chloride phosphorus oxychloride, two -2- xenyls phosphoryl chloride phosphorus oxychlorides, two -3- xenyls phosphoryl chloride phosphorus oxychlorides, two -4- xenyl phosphoryl chloride phosphorus oxychlorides etc., in them
Any two or more mixture.
In addition, as the preferred concrete example of the dihalo phosphoric acid ester shown in aforementioned formula (Ib), such as benzene can be included
Base either dichlorophosphate, a tolyl either dichlorophosphate, p-methylphenyl either dichlorophosphate, 2,6- xylyls either dichlorophosphate, 3,
The xylyl either dichlorophosphates such as 5- xylyls either dichlorophosphate, 2,5- xylyl either dichlorophosphates；Isopropyl phenyl two
Chlorine phosphate, isobutyl phenenyl either dichlorophosphate, tert-butyl-phenyl either dichlorophosphate, 1- naphthyls either dichlorophosphate, 2- naphthyls two
Chlorine phosphate, 2- xenyls either dichlorophosphate, 3- xenyls either dichlorophosphate, 4- xenyl either dichlorophosphates etc..
According to the present invention, by make such monohaloalkyl phosphoric acid ester with selected from having 1 primary amino radical and/or secondary in molecule
There are at least a kind amine compounds in the diamine compound of 2 primary amino radicals and/or secondary amino group in the monoamine compound and molecule of amino
There is de-hydrogen halide, condensation reaction occur in thing, can be relative with monohaloalkyl phosphoric acid ester used and amines used
Should ground acquisition target phosphoric ester amides class.
In addition, according to the present invention, when dihalo phosphoric acid ester as described above is used as into halophosphoric acid esters, by making it
There is de-hydrogen halide with the monoamine compound in molecule with 1 primary amino radical and/or secondary amino group, condensation reaction occur,
Target phosphoric ester amides class can be accordingly obtained with dihalo phosphoric acid ester used and monoamine compound used.
On the monoamine compound used in the present invention, there is the monoamine of 1 primary amino radical and/or secondary amino group in above-mentioned molecule
Compound can be any number of in aromatic series monoamine compound and aliphatic monoamine compound, similarly, have in above-mentioned molecule
The diamine compound for having 2 primary amino radicals and/or secondary amino group can also be aromatic diamine compound and aliphatic diamine compound
In it is any number of.
In the present invention, aromatic series monoamine compound is preferably represented with formula (IIa).
(in formula, Ar1Represent aryl, Y1Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y1For
During aryl, Y1With Ar1Can be the same or different.).
Above-mentioned aryl Ar1And Y1During for aryl, these aryl Ar1And Y1Preferably carbon number is 6~12 aryl, this
A little aryl have one or more alkyl, the preferably alkyl of carbon number 1~6, foregoing optionally on aromatic rings as substitution base
Such is inactive substitution base to reaction.Accordingly, as this aryl, for example, can include phenyl, tolyl, dimethylbenzene
Base, trimethylphenyl, methoxyphenyl, naphthyl, methyl naphthyl, xenyl, methyl biphenyl etc..
Above-mentioned Y1During for alkyl, this alkyl is preferably carbon number 1~20, more preferably 1~12, particularly preferred 1~6
Alkyl, the alkyl of carbon number more than 3 can be straight-chain, or branched, as this alkyl, for example, can include
Methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, nonyl, dodecyl etc..In addition, alkyl is optionally with foregoing such
To reaction for inactive heterocyclic radical as substitution base.
Above-mentioned Y1During for alkenyl, this alkenyl is preferably the alkenyl that carbon number is 2~6, for example, can include
Pi-allyl, isopropenyl etc..In addition, alkenyl optionally have it is foregoing to reaction for inactive heterocyclic radical as substitution
Base.
Above-mentioned Y1During for cycloalkyl, this cycloalkyl is optionally have carbon number 1~6 on the carbon atom for forming ring
Alkyl, it is foregoing to reaction for the total carbon atom number of inactive substitution base is 5~20, is preferably 5~12 cycloalkyl,
Accordingly, as the concrete example of this cycloalkyl, can for example include cyclopenta, methylcyclopentyl, cyclohexyl, methylcyclohexyl,
Dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl etc..
In addition, above-mentioned Y1During for aryl alkyl, as this aryl alkyl, for example, benzyl, phenylethyl etc. can be included.
Aryl alkyl optionally on aromatic rings with carbon number 1~6 alkyl, it is foregoing to reaction be inactive substitution
Base.
Therefore, in the present invention, as preferred aromatic series monoamine compound, can for example include aniline, ortho-aminotoluene,
Meta-aminotoluene, para-totuidine, 23 dimethyl aniline, 2,4- dimethylanilines, 3,4- dimethylanilines, 2,6- dimethylanilines
Etc. dimethyl benzene amine；Nitrobenzene amine, 1- naphthylamines, 2- naphthylamines, 2- xenylamines, 3- xenylamines, 4- xenylamines,
Methylphenylamine, N-ethylaniline, aminopyridines etc..
In the present invention, aromatic diamine compound is preferably represented with formula (IIb).
(in formula, Ar2Represent respectively with molecule in 2 nitrogen atom bondings the divalent group comprising aromatic rings, Y2And Y3Respectively
From independently expression hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y2With Y3Can with it is identical can not also
Together.).
As described above, in the present invention, the above-mentioned divalent group Ar with aromatic rings2In the molecule for forming diamine compound
2 nitrogen atom bondings, above-mentioned aromatic rings optionally thereon with carbon number 1~6 alkyl, it is foregoing to reaction be
Inactive substitution base.
Therefore, this divalent group Ar with aromatic rings2It is preferred a kind of be arlydene, as preferred concrete example,
The optionally alkyl with carbon number 1~6, the foregoing neighbour Asia benzene to reacting for inactive substitution base can be included
Base, metaphenylene, to phenylene, naphthylene, biphenylene etc..
In the present invention, as the preferred divalent group Ar with aromatic rings2Another kind, logical formula (III) institute can be included
Group for showing etc..
(in formula, divalent group Z is represented selected from alkylidene, ring alkylidene, oxygen atom, sulphur atom, disulfide group, sulfoxide group, sulphur
Divalent group in acyl group and carbonyl.)
In the present invention, such divalent group Ar2Arlydene among, particularly preferably using above-mentioned divalent group Z for for example
The arlydene of alkylidene, oxygen atom.
When divalent group Z is alkylidene, the alkylidene optionally has the aryl of phenyl etc as substitution base.Divalent group Z
During for alkylidene, this preferred carbon number of alkylidene is 1~6 scope, for example, can include methylene, ethylidene, ethylidene
Base, dimethyl methine, Methylethyl methine etc.., as the alkylidene of substitution base, phenyl can be included as with phenyl
Methine, diphenyl methine etc..
When divalent group Z is ring alkylidene, can include optionally has carbon number 1~6 on the carbon atom for forming ring
Alkyl, it is foregoing to reaction for it is inactive substitution base cyclohexylene, cyclohexylidene base.
Above-mentioned Y2And Y3Can independently of one another with foregoing Y1It is identical, alternatively, it is also possible to independently of one another with aforesaid aryl
Ar1It is identical.Therefore, above-mentioned Y2With Y3Can be with mutually the same, it is also possible to different.
Therefore, in the present invention, as preferred aromatic diamine compound, for example, o-phenylenediamine, isophthalic can be included
The diaminotoluene classes such as diamines, p-phenylenediamine, 2,4 di amino toluene, 2,6- diaminotoluenes；The diaminos such as 1,8- diaminonaphthalenes
Base naphthalenes；The benzidine class such as 4,4 '-benzidine；Double (4- aminophenyls) second of double (4- aminophenyls) methane, 1,1-
Double (4- aminophenyls) ethane of alkane, 1,2-, double (4- aminophenyls) propane of 1,1-, 2,2- double (4- aminophenyls) propane, 1,1-
Double (4- aminophenyls) butane, 4,4 '-diaminodiphenyl ether, 4,4 '-DADPS, diamino-pyridine class etc..
In addition, in the present invention, aliphatic monoamine compound is preferably represented with formula (IVa).
(in formula, Ay1Represent alkyl, alkenyl, cycloalkyl or aryl alkyl, Y4Represent hydrogen atom, alkyl, alkenyl, ring
Alkyl or aryl alkyl, or, Ay1With Y45~7 yuan of rings can be collectively forming, now, above-mentioned ring can comprising oxygen atom and/or
Nitrogen-atoms is used as the atom for forming the ring.Wherein, when the atom for forming ring is nitrogen-atoms, the nitrogen-atoms is without bonded thereto
Hydrogen atom.)
Above-mentioned group Ay1During for alkyl, it is 1~20, more preferably 1~12, particularly preferred 1 that the alkyl is preferably carbon number
~6 alkyl, the alkyl of carbon number more than 3 can be straight-chain, or branched, as this alkyl, for example may be used
Include methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, nonyl, dodecyl etc..In addition, abovementioned alkyl optionally has
Have it is foregoing to reaction for inactive heterocyclic radical as substitution base.
Above-mentioned Ay1During for alkenyl, this alkenyl is preferably the alkenyl that carbon number is 2~6, for example, can include
Pi-allyl, isopropenyl etc..In addition, it is inactive heterocyclic radical conduct to reaction that above-mentioned alkenyl optionally has foregoing
Substitution base.
Above-mentioned Ay1During for cycloalkyl, this cycloalkyl is optionally have carbon number 1~6 on the carbon atom for forming ring
Alkyl, it is foregoing to reaction for it is inactive substitution base total carbon atom number 5~20, be preferably 5~12 cycloalkyl,
Accordingly, as the concrete example of this cycloalkyl, can for example include cyclopenta, methylcyclopentyl, cyclohexyl, methylcyclohexyl,
Dimethylcyclohexyl, trimethylcyclohexyl, ethylcyclohexyl etc..
Above-mentioned Ay1During for aryl alkyl, as this aryl alkyl, for example, benzyl, phenylethyl etc. can be included.
Therefore, in the present invention, as aliphatic monoamine compound, for example, methylamine, ethamine, n-propylamine, isopropyl can be included
Amine, n-butylamine, isobutyl amine, tert-butylamine, hexylamine, heptyl amice, 2 ethyl hexylamine, cyclohexylamine, piperidines, benzylamine, dimethylamine, diethylamine,
Di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, two tert-butylamines, diamylamine, dihexylamine, two (2- ethylhexyls) amine,
The methyl piperazines such as dicyclohexyl amine, dibenzylamine, allylamine, morpholine, diallylamine, 1- amino-ethyls -2-methylimidazole, pipecoline
Pyridine class；Any two or more mixture in them.
In addition, in the present invention, aliphatic diamine compound is preferably represented with formula (IVb).
(in formula, Ay2Represent alkylidene or ring alkylene with aromatic series base optionally on carbon atom or between carbon atom
Base, Y5And Y6Hydrogen atom, alkyl, alkenyl, cycloalkyl or aryl alkyl are represented independently of one another, or, Ay2With Y5Can be total to
With 5~7 yuan of rings of formation, or Ay2With Y65~7 yuan of rings, or Ay can be collectively forming2With Y5With Y65~7 can be collectively forming
Yuan of rings.)
Above-mentioned group Ay2During for alkylidene, the alkylidene optionally has the aryl of phenyl etc as substitution base.Group Ay2
During for alkylidene, this preferred carbon number of alkylidene is 1~6 scope, for example, can include methylene, ethidine, diformazan
Base methine, Methylethyl methine etc..As with phenyl as substitution base alkylidene, can include phenyl methine,
Diphenyl methine, 1- phenyl-ethylenes, 1,2- diphenylethylenes etc..
Above-mentioned group Ay2During for ring alkylidene, as this ring alkylidene, can include and optionally form the carbon atom of ring
The upper alkyl with carbon number 1~6, it is foregoing be cyclohexylene, the cyclohexylidene base of inactive substitution base to reaction.
Above-mentioned group Ay2During for aryl alkyl, as this aryl alkyl, benzyl, phenylethyl can be included.
In addition, optionally the alkylidene with aromatic group is preferably the divalent shown in logical formula (V) between above-mentioned carbon atom
Group.
(in formula, Y represents that it is the Asia virtue of inactive substitution base to reaction optionally to have on aromatic rings foregoing
Base, A1And A2The alkylidene of carbon number 1~6 is represented independently of one another.)
In divalent group shown in above-mentioned logical formula (V), above-mentioned arlydene is, for example, phenylene, naphthylene, biphenylene etc.,
Preferably phenylene, the above-mentioned preferred carbon number of alkylidene is 1~4, as concrete example, can include methylene, ethylidene, Asia
Propyl group, trimethylene, tetramethylene etc..
Accordingly, as the preferred concrete example of the divalent group shown in above-mentioned logical formula (V), for example, can include following group.
Therefore, in the present invention, as aliphatic diamine compound, for example, ethylenediamine, propane diamine, fourth two can be included
Double (amino methyl) hexamethylenes of amine, 1,5- pentanediamines, 1,6- hexamethylene diamines, 1,3-, double (amino methyl) hexamethylenes of 1,4-, 1,3- are double
Double (amino methyl) benzene of double (2,2 '-amino-ethyl) benzene of (2,2 '-amino-ethyl) benzene, 1,4-, piperazine, 4- amino piperidines, 1,3-,
2- methyl -4- imidazolines etc..
According to the present invention, as it was previously stated, by making monohaloalkyl phosphoric acid ester and being selected from monoamine compound and diamine compound
In at least a kind amines occur de-hydrogen halide, i.e. generation condensation reaction, can with monohaloalkyl phosphoric acid ester used and
Amines used accordingly obtains target phosphoric ester amides class.
In addition, according to the present invention, as it was previously stated, be used as halophosphoric acid esters by by dihalo phosphoric acid ester, make its with
There is de-hydrogen halide, condensation reaction occur in monoamine compound, can be with dihalo phosphoric acid ester used and monoamine used
Compound phase accordingly obtains target phosphoric ester amides class.
In the reaction of such halophosphoric acid esters and amines, according to the present invention, by making relative to 1 equivalent
Halophosphoric acid esters are more than 0.5 equivalent, are preferably the above-mentioned amines and its temperature more than 130 DEG C of 0.8~1.2 equivalent
Reacted under degree, corresponding phosphoric ester amides class can be obtained with high yield relative to amines.
Herein, in the present invention, 1 equivalent of halophosphoric acid esters refer to 1 mole of the halophosphoric acid esters divided by
Value obtained from the halogen atom number that the halophosphoric acid esters have, 1 equivalent of amines refers to the amines 1
Primary amino radical and value obtained from the quantity of secondary amino group that mole has divided by the amines.
Thus, for example, 1 equivalent of diphenyl phosphoryl chloride is its 1 mole, 1 equivalent of phenyl dichloro phosphate be its 0.5
Mole.In addition, aniline has 1 primary amino radical, piperidines with 1 secondary amino group, therefore its 1 equivalent is its 1 mole.Benzene two
Amine, piperazine have 2 primary amino radicals and secondary amino group in the molecule respectively, therefore its 1 equivalent is its 0.5 mole.
In the method for the invention, when halophosphoric acid esters is reacted with amines, reaction dissolvent not necessarily must
Must use, but in order that reaction be smoothed out and easily carry out reacted post processing, preferably use boiling point for 130 DEG C with
On reaction dissolvent.When so using reaction dissolvent, its lower limit amount is not particularly limited, be commonly angled relative to used by 1 weight portion
Halophosphoric acid esters are more than 0.5 weight portion, are preferably more than 1 weight portion.On the other hand, the upper limit amount of reaction dissolvent used from
From the viewpoint of volumetric efficiency, halophosphoric acid esters used by 1 weight portion are commonly angled relative to below 5 weight portions, to be preferably 2 weight
Below part.
According to the present invention, by the halophosphoric acid esters of aforementioned ratio and amines generally in normal temperature or as needed slightly
It is micro- be heated to 50 DEG C or so at a temperature of, preferably put into reaction vessel together with reaction dissolvent, start reaction, exist thereafter
Reacted at a temperature of more than 130 DEG C, preferably under the reflux temperature of reaction dissolvent used.
It is a feature of the present invention that including：When the halophosphoric acid esters and amines for making aforementioned ratio react,
Reacted at a temperature of more than 130 DEG C, that is, be included in the operation reacted at a temperature of more than 130 DEG C.
The method of the present invention is not limited, if showing a preferred embodiment of the method for the present invention, in normal temperature or
To amines and reaction dissolvent is put into reaction vessel at a temperature of being slightly moderately heated to 50 DEG C or so as needed, make amine compounds
Thing is dissolved in reaction dissolvent, then, side stirring gained amines solution, side in the amines solution lentamente to adding halogen
Substituted phosphate class.During so lentamente adding halophosphoric acid esters in amines solution, from amines solution
The middle halogen acid salt for separating out target phosphoric ester amides class and amines, reactant mixture is formed and includes phosphoric ester amides class and amine
The dispersion liquid of the halogen acid salt of compound.
Then, if terminate addition halophosphoric acid esters, by reactant mixture be slowly warmed to initial reaction temperature,
The reflux temperature of i.e. more than 130 DEG C of temperature, reaction dissolvent preferably used, while keeping the temperature, side continues to react 30 minutes
~a few houres.During untill reactant mixture so is heated into initial reaction temperature, although also depend on amination used
The species of compound and halophosphoric acid esters, but for reactant mixture, generally exceed about 100 from the temperature of reactant mixture~
120 DEG C of moment, phosphoric ester amides class dissolves in reaction dissolvent, and formation has only separated out the halogen acid salt of amines
Dispersion liquid.
Thereafter, continue to heat the temperature more than initial reaction temperature, i.e. 130 DEG C to reactant mixture, be preferably
When untill the reflux temperature of reaction dissolvent used, in the halogen acid salt of the initial stage undissolved amines in reaction dissolvent of reaction
Solid matter also reach about 130 DEG C since the temperature of reactant mixture moment with reaction carrying out and gradually decrease,
The final period of the reaction under desired reaction temperature, the halogen acid salt of amines all disappears, and reactant mixture turns into equal
Even and transparent solution.In this way, when reactant mixture turns into uniform and transparent solution, terminating reaction.
Therefore, in the present invention, it is necessary that as described above, being obtained in phosphoric ester amides class is dissolved in reaction dissolvent
To after the dispersion liquid of the halogen acid salt for only having separated out amines, continue to react until in desired reaction temperature, i.e. 130 DEG C
More than temperature, the halogen acid salt that is preferably amines under the reflux temperature of reaction dissolvent used all disappear, reaction mixing
Untill thing forms uniform and transparent solution, i.e., untill reaction terminates.So up to the temperature more than 130 DEG C, preferably
For the halogen acid salt whole disappearance of amines, reactant mixture form uniform and transparent under the reflux temperature of reaction dissolvent used
Solution untill, i.e., although the time untill reaction terminates also depend on the kind of amines used and halophosphoric acid esters
Class, but the usually scope of 30 minutes~a few houres.
In the present invention, amines is made to be not limited to the mode that halophosphoric acid esters react above-mentioned illustrated
Mode, amines is dissolved in reaction dissolvent and be heated to 100~130 DEG C or so, it is another
Aspect similarly makes halophosphoric acid esters be dissolved in reaction dissolvent and is heated to 100~130 DEG C or so, to above-mentioned amines
Solution in add halophosphoric acid esters solution, react it.
As described later, it is nonactive to being circulated in reaction vessel it is preferred according the present invention, that during above-mentioned reaction
Gas, air, produced hydrogen halide is removed to outside reaction system.
In the present invention, although the upper limit of reaction temperature also depends on the reaction dissolvent when using reaction dissolvent, but logical
It is often less than 250 DEG C, preferably less than 240 DEG C.Especially, in the present invention, although reaction temperature is when using reaction dissolvent
Depending on the reaction dissolvent, but preferably 140~220 DEG C of scope in practical.
As the reaction dissolvent that above-mentioned boiling point is more than 130 DEG C, for example preferably using dimethylbenzene, trimethylbenzene, cumene,
The aromatic hydrocarbon solvents such as pseudocumene, solvent naphtha, so-called naphtha series solvent；The aliphatic hydrocarbon of isoparaffin series solvent etc
Solvent；The halogenated aromatic hydrocarbon solvent such as monochlorobenzene, dichloro-benzenes, trichloro-benzenes；The aromatic ether solvent such as diphenyl ether；Or theirs is mixed
Compound.
In the present invention, so that various aromatic hydrocarbons are as main component and are referred to as solvent naphtha, naphtha series solvent
The organic solvent that more than 130 DEG C of boiling point is included in above-mentioned aromatic hydrocarbon solvents, in addition, using isoparaffin system hydrocarbon as mainly into
Point and the organic solvent of more than 130 DEG C of boiling point be included in above-mentioned aliphatic hydrocarbon solvent.
The manufacture method of phosphoric ester amides class of the invention, is not made by the halophosphoric acid esters relative to 1 equivalent
With excessive amines, but according to preferred embodiment using 0.8~1.2 equivalent, more preferably use substantially 1 equivalent, so as to
It is enough that target phosphoric ester amides are obtained with high yield relative to amines.It is believed that its reason is as described below.
I.e., first, in the halophosphoric acid esters of the amines using 1 equivalent and 1 equivalent, above-mentioned amines is being made
Also worked as hydrogen halides capturing agent while for reactive material and promote reaction, therefore in the above-mentioned amines of 1 equivalent
Among the halophosphoric acid esters of 1 equivalent, even if the halogenated phosphate of the amines of 0.5 equivalent and 0.5 equivalent is relatively low
At a temperature of can also react, generate corresponding phosphoric ester amides class.But, now remaining 0.5 equivalent amines capture by
The hydrogen halides of above-mentioned reaction generation, forms halogen acid salt, therefore in the state of such halogen acid salt, it is impossible to it is remaining
The halophosphoric acid esters of 0.5 equivalent react.Thus, by further improving reaction temperature, hydrogen halide is from above-mentioned amine
Depart from the halogen acid salt of compound and go to outside reaction system, amines reverts to free amines again, therefore
It reacts with halophosphoric acid esters.It is considered that：The hydrogen halides for now generating will not be by amine under the reaction condition of high temperature
Compound capture and go directly to outside reaction system, even if or captured by amines, under the reaction condition of high temperature, halogenation
Hydrogen departs from similarly from halogen acid salt and goes to outside reaction system.
Therefore, in the manufacture of phosphoric ester amides class of the invention, in order to will be by halophosphoric acid esters and amines
Condensation reaction and the hydrogen halide that generates remove to outside reaction system, reaction system needs to be communicated to outside reaction system,
Especially, according to the present invention, it is generally desirable to by will from the halogen acid salt of amines depart from hydrogen halide forcibly
Outside removal to reaction system, so as to promote being smoothed out for reaction.
Therefore it is preferred according to the present invention that, in the reaction of halophosphoric acid esters and amines, to reaction vessel
In be blown into the non-active gas such as nitrogen, helium, argon gas, carbon dioxide, air, under this non-active gas air-flow or air gas
Flow down and reacted or reacted in the case where decompression is aspirated.
So operate, after halophosphoric acid esters is reacted with amines, in order to divide from gained reactant mixture
Target phosphoric ester amides class is separated out, for example, is cooled down gained reactant mixture, separate out product, its leaching then, is used
The aqueous alkali cleaning of aqueous acid, the sodium carbonate of hydrochloric acid etc etc, is then cleaned with hot water, removes unreacting substance, and
It is dried such that it is able to obtain target phosphoric ester amides class.Thereafter, can use as needed the lower alcohols such as methyl alcohol, ethanol or
Acetone is cleaned, or, carry out recrystallization treatment furthermore with hot alcohol.
According to the present invention, so operate, can accordingly obtain target with foregoing halophosphoric acid esters and amines
Phosphoric ester amides class.
That is, by making the monohaloalkyl phosphoric acid ester shown in aforementioned formula (Ia) with the aromatic series shown in aforementioned formula (IIa)
Monoamine compound reacts, and the phosphoric ester amides class shown in formula (VIa) is obtained in that, in addition, by making aforementioned formula
(Ia) the monohaloalkyl phosphoric acid ester shown in reacts with the aromatic diamine compound shown in aforementioned formula (IIb), can obtain
Obtain the phosphoric ester amides class shown in formula (VIb).
Similarly, by making the monohaloalkyl phosphoric acid ester shown in aforementioned formula (Ia) with the fat shown in aforementioned formula (IVa)
Fat race monoamine compound reacts, and is obtained in that the phosphoric ester amides class shown in formula (VIIa), in addition, foregoing logical by making
Monohaloalkyl phosphoric acid ester shown in formula (Ia) reacts with the aliphatic diamine compound shown in aforementioned formula (IVb), can
Obtain the phosphoric ester amides class shown in formula (VIIb).
And then, by making the dihalo phosphoric acid ester shown in aforementioned formula (Ib) with the fragrance shown in aforementioned formula (IIa)
Race's monoamine compound reacts, and is obtained in that the phosphoric ester amides class shown in formula (VIIIa), similarly, foregoing by making
Dihalo phosphoric acid ester shown in formula (Ib) reacts with the aliphatic monoamine compound shown in aforementioned formula (IVa), energy
Enough obtain the phosphoric ester amides class shown in formula (VIIIb).
Therefore, in the present invention, as the phosphoric ester amides class shown in formula (VIa), for example, following phosphates can be included
Amide-type.
As the phosphoric ester amides class shown in formula (VIb), for example, can include following phosphoric ester amides classes.
As the phosphoric ester amides class shown in formula (VIIa), for example, can include following phosphoric ester amides classes.
As the phosphoric ester amides class shown in formula (VIIb), for example, can include following phosphoric ester amides classes.
As the phosphoric ester amides class shown in formula (VIIIa), for example, can include following phosphoric ester amides classes.
As the phosphoric ester amides class shown in formula (VIIIb), for example, can include following phosphoric ester amides classes.
Embodiment
Being exemplified below embodiment illustrates the present invention, but the present invention not by any restriction of these embodiments.Hereinafter, melt
Put the value that the peak initially occurred when being and being heated up with 20 DEG C/min in being resurveyed calmly by differential hot-hot is obtained.
Embodiment 1
At normal temperatures to aniline 9.8g (0.105 mole) and trimethylbenzene 35mL is put into round-bottomed flask, it is dissolved in aniline
Trimethylbenzene.Resulting solution is stirred on side, while the solution is maintained at into less than 40 DEG C, cost 10 minutes in the solution to being slowly added dropwise two
Diphenylphosphoryl chlorine 26.9g (0.100 mole).Now, anilino- diphenyl phosphoester and aniline hydrochloric acid are separated out from above-mentioned solution
Salt, reactant mixture turns into the dispersion liquid comprising above-mentioned precipitate.
After completion of dropwise addition, reactant mixture is spent and is to slowly warm up to 170~180 DEG C within 30 minutes, while trimethylbenzene is flowed back,
While being reacted 1 hour at temperature same as described above.Since the moment of the temperature more than 100 DEG C of reactant mixture, anilino-
Diphenyl phosphoester is dissolved in trimethylbenzene, as the dispersion liquid for only having separated out anilinechloride.The initial stage of reaction is undissolved in three
The solid matter of the anilinechloride of toluene is also when the temperature of reactant mixture reaches more than 130 DEG C with the carrying out of reaction
It is slow to reduce.In the final period of reaction, the solid matter of anilinechloride disappears, and reactant mixture turns into uniform and transparent molten
Liquid.
During above-mentioned reaction, to the nitrogen that circulated in round-bottomed flask, produced hydrogen chloride gas 3.0g is reclaimed.Reaction
After end, reactant mixture is cooled to room temperature and precipitate is obtained.
The precipitate is filtered by suction, after being cleaned with diluted hydrochloric acid aqueous solution, saturated aqueous sodium carbonate and hot water successively, makes it
Dry, obtain anilino- diphenyl phosphoester 27.8g.It is 81.5% relative to the yield of aniline.Fusing point is 131.5 DEG C of (Japan
The fusing point that JP 49-72346 publications are recorded is 130 DEG C).
Embodiment 2
In embodiment 1, using aniline 11.2g (0.120 mole), in addition same operation, obtains anilino- hexichol
Base phosphate 30.5g.It is 78.2% relative to the yield of aniline.Fusing point is 132.0 DEG C.
Embodiment 3
In embodiment 1, using aniline 9.30g (0.100 mole) and diphenyl phosphoryl chloride 33.6g (0.125 mole), remove
Equally operated outside this, obtain anilino- diphenyl phosphoester 29.5g.It is 72.6% relative to the yield of diphenyl phosphoryl chloride.
Fusing point is 131.2 DEG C.
Embodiment 4
In embodiment 1, using aniline 11.3g (0.122 mole) and diphenyl phosphoryl chloride 23.7g (0.088 mole) and
Phenyl dichloro phosphate 2.9g (0.014 mole), in addition same operation, obtains anilino- diphenyl phosphoester and diphenylamines
The mixture 30.1g of base phenyl phosphate ester.Wherein, the analysis result based on liquid chromatography is, the single benzene in said mixture
The content of aminate is 86.6 weight %.The yield relative to aniline of said mixture is 75.9%.Fusing point is 130.8 DEG C.
Embodiment 5
In embodiment 1, diphenylphosphine is replaced using two (2,6- xylyl) phosphoryl chloride phosphorus oxychloride 32.5g (0.100 mole)
Acyl chlorides, in addition same operation, obtains anilino- two (2,6- xylyl) phosphate 32.4g.Relative to the yield of aniline
It is 81.0%.Fusing point is 127.2 DEG C.
Embodiment 6
In embodiment 1, isoparaffin series solvent (the ISOPAR L that Exxon Mobil Corporation are manufactured) is used
It is used as solvent instead of trimethylbenzene, the temperature of reactant mixture when reacting is set to 190~200 DEG C, in addition same behaviour
Make, obtain anilino- diphenyl phosphoester 29.2g.It is 85.6% relative to the yield of aniline.Fusing point is 133.2 DEG C.
Embodiment 7
In embodiment 1, it is used as solvent instead of trimethylbenzene using diphenyl ether, by the temperature of reactant mixture when reacting
200~220 DEG C are set to, in addition same operation, obtains anilino- diphenyl phosphoester 26.4g.Relative to the yield of aniline
It is 77.4%.Fusing point is 130.8 DEG C.
Embodiment 8
In embodiment 1, it is used as solvent instead of trimethylbenzene using dimethylbenzene, by the temperature of reactant mixture when reacting
140~145 DEG C are set to, will be set in the reaction time 2 hours, in addition same operation, obtains anilino- diphenyl phosphoester
25.7g.Relative to the yield 75.3% of aniline.Fusing point is 130.9 DEG C.
Embodiment 9
In embodiment 1, aniline is replaced using morpholine 9.1g (0.105 mole), in addition same operation, obtains
Quinoline is for diphenyl phosphoester 23.9g.It is 71.4% relative to the yield of morpholine.76.1 DEG C of (Japanese Unexamined Patent Publication 2000-154277 of fusing point
71 DEG C of the fusing point that number publication is recorded).
Embodiment 10
In embodiment 1, replace aniline using piperazine 4.5g (0.052 mole), use different alkane as hereinbefore
Hydrocarbon is used as solvent instead of trimethylbenzene, the temperature of reactant mixture when reacting is set into 190~200 DEG C, in addition equally
Operation, obtains double (diphenyl phosphoester) 18.5g of Isosorbide-5-Nitrae-piperazinyl.It is 64.3% relative to the yield of piperazine.Fusing point is 184 DEG C
(fusing point that Japanese Unexamined Patent Publication 2000-327834 publications are recorded is 184 DEG C).
Embodiment 11
In embodiment 1, aniline is replaced using m-phenylene diamine (MPD) 5.7g (0.053 mole), in addition same operation, obtains
To double (diphenylphosphine amino) benzene (1,3-bis (diphenyl-phosphoroamino) benzene) 21.6g of 1,3-.Relative to
The yield of m-phenylene diamine (MPD) is 71.5%.Fusing point is 182.3 DEG C, and (J.Chem.Soc. (C), 1971 fusing points recorded are 183~184
℃)。
Embodiment 12
In embodiment 1, replace aniline using p-phenylenediamine 5.7g (0.053 mole), (gone out using naphtha series solvent
The IPZOLE 150 of Guang Xingchan Co., Ltd. manufacture) replace trimethylbenzene, the temperature of reactant mixture when reacting is set to 200
DEG C, will be set in the reaction time 4 hours, in addition same operation, obtains Isosorbide-5-Nitrae-bis- (diphenylphosphine amino) benzene 22.9g.Relatively
In p-phenylenediamine yield be 75.9%.210.3 DEG C of fusing point (J.Chem.Soc. (C), 1971 fusing points 210~211 recorded
℃)。
Embodiment 13
In embodiment 12, p-phenylenediamine is replaced using 4,4 '-diaminodiphenyl-methane 10.4g (0.053 mole),
To be set in the reaction time 5 hours, in addition same operation, obtains 4,4 '-bis- (diphenylphosphine amidophenyl) methane
30.8g.It is 88.6% relative to the yield of 4,4 '-diaminodiphenyl-methane.Fusing point is 186.5 DEG C of (Japanese Unexamined Patent Publication 2003-
The fusing point of No. 238580 publication records is 194 DEG C).
Comparative example 1
Aniline 30.0g (0.323 mole) and toluene 45mL are put into round-bottomed flask, while being stirred at room temperature, side is upward
State and be slowly added dropwise diphenyl phosphoryl chloride 40.8g (0.152 mole) in mixture.After completion of dropwise addition, by the temperature of reactant mixture
80 DEG C are set to, after continuing to stir 1 hour, are cooled down, so as to obtain precipitate.The leaching precipitate, dries it after washing,
Obtain anilino- diphenyl phosphoester 45.1g.It is 43.0% relative to the yield of aniline.Fusing point is 131.6 DEG C.
Comparative example 2
In embodiment 1, diphenyl phosphoryl chloride is added dropwise at room temperature, after the completion of dropwise addition, reactant mixture is heated up,
It is directly set to react at room temperature 1 hour, in addition same operation, obtains anilino- diphenyl phosphoester 13.4g.Relative to
The yield of aniline is 39.3%.Fusing point is 131.1 DEG C.
Claims (13)
1. it is a kind of manufacture phosphoric ester amides class method, it is characterised in that
(A) make selected from the monohaloalkyl phosphoric acid ester shown in formula (Ia) and the dihalo phosphoric acid ester shown in formula (Ib) extremely
Few a kind of halophosphoric acid esters with there is primary amino radical selected from having in molecule in the monoamine compound and molecule of primary amino radical or secondary amino group
And/or there is de-hydrogen halide at least a kind amines in the diamine compound of secondary amino group, or,
(B) make as the above-mentioned dihalo phosphoric acid ester and the monoamine with primary amino radical or secondary amino group in molecule of halophosphoric acid esters
Change
There is de-hydrogen halide in compound,
So as to manufacture the phosphoric ester amides class corresponding to above-mentioned halophosphoric acid esters,
In the method, including：Relative to the above-mentioned halophosphoric acid esters of 1 equivalent, make the above-mentioned amine compounds of 0.8~1.2 equivalent
Thing more than 130 DEG C at a temperature of react,
In above-mentioned formula, R1、R2And R3Represent that it is in the reaction the alkyl of inactive substitution base optionally to have independently of one another, appoint
Choosing have in the reaction for it is inactive substitution base cycloalkyl, optionally have in the reaction for it is inactive substitution base aryl
Or it be in the reaction the aryl alkyl of inactive substitution base optionally to have, X represents halogen atom.
2. method according to claim 1, wherein, make monohaloalkyl phosphoric acid ester shown in the formula (Ia) with as amine
Aromatic series monoamine compound shown in the formula (IIa) of compound reacts, so as to manufacture the phosphate shown in formula (VIa)
Amide-type,
In formula, Ar1Represent aryl, Y1Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y1It is aryl
When, Y1With Ar1Can be the same or different,
3. method according to claim 1, wherein, make monohaloalkyl phosphoric acid ester shown in the formula (Ia) with as amine
Aromatic diamine compound shown in the formula (IIb) of compound reacts, so as to manufacture the phosphate shown in formula (VIb)
Amide-type,
In formula, Ar2Represent respectively with molecule in 2 nitrogen atom bondings the divalent group comprising aromatic rings, Y2And Y3Each solely
On the spot represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y2With Y3Can be the same or different,
4. method according to claim 1, wherein, make the monohaloalkyl phosphoric acid ester and formula shown in the formula (Ia)
(IVa) the aliphatic monoamine compound shown in reacts, so that the phosphoric ester amides class shown in formula (VIIa) is manufactured,
In formula, Ay1Represent alkyl, alkenyl, cycloalkyl or aryl alkyl, Y4Represent hydrogen atom, alkyl, alkenyl, cycloalkyl or
Aryl alkyl, or, Ay1With Y45~7 yuan of rings can be collectively forming, now, above-mentioned ring can include oxygen atom and/or nitrogen-atoms
As the atom for forming the ring, wherein, when the atom for forming ring is nitrogen-atoms, the nitrogen-atoms is former without hydrogen bonded thereto
Son,
5. method according to claim 1, wherein, make monohaloalkyl phosphoric acid ester shown in the formula (Ia) with as amine
Aliphatic diamine compound shown in the formula (IVb) of compound reacts, so as to manufacture the phosphoric acid shown in formula (VIIb)
Esteramides class,
In formula, Ay2Represent alkylidene or ring alkylidene with aromatic group, Y optionally on carbon atom or between carbon atom5With
Y6Hydrogen atom, alkyl, alkenyl, cycloalkyl or aryl alkyl are represented independently of one another, or, Ay2With Y55 can be collectively forming
~7 yuan of rings, or Ay2With Y65~7 yuan of rings, or Ay can be collectively forming2With Y5With Y65~7 yuan of rings can be collectively forming,
6. method according to claim 1, wherein, make dihalo phosphoric acid ester shown in the formula (Ib) with as amine
Aromatic series monoamine compound shown in the formula (IIa) of compound reacts, so as to manufacture the phosphoric acid shown in formula (VIIIa)
Esteramides class,
In formula, Ar1Represent aryl, Y1Represent hydrogen atom, alkyl, alkenyl, cycloalkyl, aryl or aryl alkyl, Y1It is aryl
When, Y1With Ar1Can be the same or different,
7. method according to claim 1, wherein, make dihalo phosphoric acid ester shown in the formula (Ib) with as amine
Aliphatic monoamine compound shown in the formula (IVa) of compound reacts, so as to manufacture the phosphoric acid shown in formula (VIIIb)
Esteramides class,
In formula, Ay1Represent alkyl, alkenyl, cycloalkyl or aryl alkyl, Y4Represent hydrogen atom, alkyl, alkenyl, cycloalkyl or
Aryl alkyl, or, Ay1With Y45~7 yuan of rings can be collectively forming, now, above-mentioned ring can include oxygen atom and/or nitrogen-atoms
As the atom for forming the ring, wherein, when the atom for forming ring is nitrogen-atoms, the nitrogen-atoms is former without hydrogen bonded thereto
Son,
8. method according to claim 1, wherein, halophosphoric acid esters and amines are made in the presence of reaction dissolvent
React.
9. method according to claim 8, wherein, reaction dissolvent is aromatic hydrocarbon, the halo selected from more than 130 DEG C of boiling point
At least a kind in aromatic hydrocarbon, aliphatic hydrocarbon and aromatic series ethers.
10. method according to claim 8, wherein, reaction dissolvent is selected from dimethylbenzene, trimethylbenzene, monochlorobenzene, dichloro
At least a kind in benzene, trichloro-benzenes and diphenyl ether.
11. methods according to claim 1, wherein, make halophosphoric acid esters with amines in air or nonactive gas
Reacted under body air-flow.
12. methods according to claim 1, wherein, halophosphoric acid esters is occurred in the case where decompression is aspirated with amines
Reaction.
13. method according to any one of claim 1~12, wherein, make halophosphoric acid esters with amines 170
Reacted at a temperature of more than DEG C.
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| CN105753900A (en) * | 2016-03-22 | 2016-07-13 | 和夏化学(太仓)有限公司 | Synthesis method of aromatic amide phosphate compound and flame retardant containing compound |
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