JP2012001475A - Method for producing nitro compound - Google Patents
Method for producing nitro compound Download PDFInfo
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- JP2012001475A JP2012001475A JP2010137173A JP2010137173A JP2012001475A JP 2012001475 A JP2012001475 A JP 2012001475A JP 2010137173 A JP2010137173 A JP 2010137173A JP 2010137173 A JP2010137173 A JP 2010137173A JP 2012001475 A JP2012001475 A JP 2012001475A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000002828 nitro derivatives Chemical class 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- -1 cyclic carbodiimide compound Chemical class 0.000 claims abstract description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical class CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 claims description 3
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical class CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 claims description 3
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical class C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 claims description 3
- FWLORMQUOWCQPO-UHFFFAOYSA-N benzyl-dimethyl-octadecylazanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 FWLORMQUOWCQPO-UHFFFAOYSA-N 0.000 claims description 3
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical class CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical group [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- QJCGFOKIXFUSST-UHFFFAOYSA-N [N+](=O)([O-])C(O)C(CO)(CO)CO.[N+](=O)([O-])C1=C(C=CC=C1)[N+](=O)[O-] Chemical class [N+](=O)([O-])C(O)C(CO)(CO)CO.[N+](=O)([O-])C1=C(C=CC=C1)[N+](=O)[O-] QJCGFOKIXFUSST-UHFFFAOYSA-N 0.000 abstract 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Substances [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract 1
- 150000005181 nitrobenzenes Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 2
- PWKNBLFSJAVFAB-UHFFFAOYSA-N 1-fluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1F PWKNBLFSJAVFAB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002704 decyl 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])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 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 2
- 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 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 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
- 239000012948 isocyanate Substances 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 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 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 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 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LZGVDNRJCGPNDS-UHFFFAOYSA-N trinitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)[N+]([O-])=O LZGVDNRJCGPNDS-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical class OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 0 CC1(*)C=CC([N+]([O-])=O)=C(*)C=C1 Chemical compound CC1(*)C=CC([N+]([O-])=O)=C(*)C=C1 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000694440 Colpidium aqueous Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 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 1
- 239000000428 dust Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001196 nonadecyl 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])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])[H] 0.000 description 1
- 125000000913 palmityl 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])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 1
- 125000002958 pentadecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明はニトロ体の製造方法に関する、さらに詳しくは特定のニトロ体の製造方法に関する。 The present invention relates to a method for producing a nitro body, and more particularly to a method for producing a specific nitro body.
ポリエステル等のエステル結合を有する化合物は、カルボキシル基等の極性基により加水分解が促進されるため、カルボキシル基の封止剤を適用して、カルボキシル基濃度を低減することが提案されている（特許文献１、特許文献２）。かかるカルボキシル基の封止剤として、カルボジイミド化合物が使用されている。
しかし、このカルボジイミド化合物は、いずれも線状の化合物であるため、使用時、揮発性のイソシアネート化合物が副生して、悪臭を発し、作業環境を悪化させるという欠点を有する。
そこで、出願人は、封止剤として、カルボキシル基と反応してもイソシアネート化合物が副生しない環状カルボジイミド化合物を見出し国際出願した（特許文献３）。しかし、この有用な環状カルボジイミド化合物およびその中間体の工業的な製造方法は確立されていない。
Since a compound having an ester bond such as polyester is accelerated by a polar group such as a carboxyl group, it has been proposed to reduce the carboxyl group concentration by applying a carboxyl group sealant (patent) Literature 1, Patent Literature 2). A carbodiimide compound is used as such a carboxyl group sealing agent.
However, since all of these carbodiimide compounds are linear compounds, a volatile isocyanate compound is produced as a by-product during use, and has a drawback of producing a bad odor and deteriorating the working environment.
Therefore, the applicant has found a cyclic carbodiimide compound as an encapsulant in which an isocyanate compound is not by-produced even if it reacts with a carboxyl group, and has filed an international application (Patent Document 3). However, an industrial production method for this useful cyclic carbodiimide compound and its intermediate has not been established.
本発明の目的は、下記式（Ａ）で表わされる化合物（Ａ）と下記式（Ｂ）で表わされる化合物（Ｂ）とを反応させて、下記式（Ｃ）で表わされるニトロ体を合成する際に、工業的により有利に適用可能な方法を用いて、反応収率を向上させることにある。 The object of the present invention is to synthesize a nitro compound represented by the following formula (C) by reacting the compound (A) represented by the following formula (A) with the compound (B) represented by the following formula (B). In this case, the reaction yield is improved by using a method that can be applied more advantageously industrially.
（式（Ａ）中、Ｒは、水素原子、炭素原子数１〜６のアルキル基である。Ｘはハロゲン原子またはニトロ基である。） (In the formula (A), R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X is a halogen atom or a nitro group.)
（式（Ｃ）中、Ｒは式（Ａ）と同じである）
化合物（Ｃ）を得るために適用される一般的な方法は、化合物（Ｂ）に脱離基を導入し、置換ｏ−ニトロフェノールと反応させる方法、および化合物（Ｂ）と置換ｏ−ハロニトロベンゼンを反応させる方法が適用可能である。
(In formula (C), R is the same as formula (A))
General methods applied to obtain the compound (C) include a method in which a leaving group is introduced into the compound (B) and reacted with a substituted o-nitrophenol, and a compound (B) and a substituted o-halonitrobenzene. The method of reacting can be applied.
特に有用なのは後者であるが、一般には非プロトン性極性溶媒下、固体塩基性化合物を作用させる方法が用いられる。非プロトン性極性溶媒とは、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン、ジメチルスルホキシドなどに代表される。これらは一般に高価であり、工業生産においては回収サイクルが必要である。しかしながら水と相溶性があり、また一般に高沸点であるため回収が困難かつ多大なエネルギーを必要とする。固体塩基性化合物とは、一般に炭酸カリウム、水素化ナトリウム、水酸化ナトリウム、水酸化カリウム等で代表されるが、潮解性や、水素発生による爆発の危険、強アルカリ性の粉じんなど取り扱いに注意を必要とする場合が多い。 The latter is particularly useful, but generally a method in which a solid basic compound is allowed to act in an aprotic polar solvent is used. The aprotic polar solvent is represented by N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and the like. These are generally expensive and require a recovery cycle in industrial production. However, since it is compatible with water and generally has a high boiling point, it is difficult to recover and requires a lot of energy. Solid basic compounds are generally represented by potassium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, etc., but care must be taken in handling deliquescence, danger of explosion due to hydrogen generation, strong alkaline dust, etc. In many cases.
本発明者らは、下記式（Ａ）で表わされる化合物（Ａ）と下記式（Ｂ）で表わされる化合物（Ｂ）とを反応させて、下記式（Ｃ）で表わされるニトロ体を合成する際、工業的により有利に適用可能な方法を用いて、反応収率を向上させる手段について検討した。その結果、反応に際し、特定の触媒とアルカリ金属水酸化物の水溶液とを組み合わせて存在させると、非プロトン性極性溶媒を用いずとも、高収率かつ高純度でニトロ体を製造可能であることを見出し、本発明を完成した。
即ち、本発明は、以下の発明を包含する。
１．下記式（Ａ）で表わされる化合物（Ａ）と下記式（Ｂ）で表わされる化合物（Ｂ）とを、相間移動触媒およびアルカリ金属水酸化物の水溶液の存在下で、反応させることを特徴とする、下記式（Ｃ）で表わされるニトロ体の製造方法。
The present inventors react a compound (A) represented by the following formula (A) with a compound (B) represented by the following formula (B) to synthesize a nitro form represented by the following formula (C). At the same time, means for improving the reaction yield were examined using a method that can be applied more advantageously industrially. As a result, in the reaction, when a specific catalyst and an aqueous solution of alkali metal hydroxide are present in combination, a nitro compound can be produced in high yield and high purity without using an aprotic polar solvent. The present invention has been completed.
That is, the present invention includes the following inventions.
1. A compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B) are reacted in the presence of a phase transfer catalyst and an aqueous solution of an alkali metal hydroxide. The manufacturing method of the nitro body represented by the following formula (C).
（式（Ａ）中、Ｒは、水素原子、炭素原子数１〜６のアルキル基である。Ｘはハロゲン原子またはニトロ基である。） (In the formula (A), R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X is a halogen atom or a nitro group.)
（式（Ｃ）中、Ｒは式（Ａ）と同じである）
２．相間移動触媒は、下記式（ｉ）で表される化合物である上記１記載の製造方法。
(In formula (C), R is the same as formula (A))
2. 2. The method according to 1 above, wherein the phase transfer catalyst is a compound represented by the following formula (i).
（式（ｉ）中、Ｒ１〜Ｒ４各々独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基から選ばれる基である。Ａ−はハロゲンアニオンである）
３．相間移動触媒は、テトラエチルアンモニウム塩、テトラブチルアンモニウム塩、トリオクチルメチルアンモニウム塩、ベンジルジメチルオクタデシルアンモニウム塩、ベンジルトリエチルアンモニウム塩、ベンジルトリメチルアンモニウム塩およびベンジルトリブチルアンモニウム塩からなる群より選ばれる少なくとも一種類の化合物である上記１記載の製造方法。
４．アルカリ金属水酸化物の水溶液は、水酸化ナトリウム水溶液または水酸化カリウム水溶液である上記１記載の製造方法。
(In formula (i), each of R1 to R4 is independently a group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. a - is a halogen anion)
3. The phase transfer catalyst is at least one selected from the group consisting of tetraethylammonium salt, tetrabutylammonium salt, trioctylmethylammonium salt, benzyldimethyloctadecylammonium salt, benzyltriethylammonium salt, benzyltrimethylammonium salt, and benzyltributylammonium salt. 2. The production method according to 1 above, which is a compound.
4). 2. The method according to 1 above, wherein the aqueous solution of the alkali metal hydroxide is an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution.
本発明の製造方法によれば、環状カルボジイミド化合物の中間体として有用な、特定のニトロ体を高収率で製造することができる。 According to the production method of the present invention, a specific nitro compound useful as an intermediate of a cyclic carbodiimide compound can be produced in a high yield.
本発明は、下記式（Ａ）で表わされる化合物（Ａ）と下記式（Ｂ）で表わされる化合物（Ｂ）とを、相間移動触媒の存在下、アルカリ金属水酸化物の水溶液の存在下で、反応させて下記式（Ｃ）で表わされるニトロ体を得ることを特徴とする。 The present invention provides a compound (A) represented by the following formula (A) and a compound (B) represented by the following formula (B) in the presence of an aqueous solution of an alkali metal hydroxide in the presence of a phase transfer catalyst. To obtain a nitro compound represented by the following formula (C).
（化合物（Ａ））
化合物（Ａ）は下記式で表される。
(Compound (A))
Compound (A) is represented by the following formula.
式（Ａ）中、Ｒは、水素原子、炭素原子数１〜６のアルキル基である。Ｘはハロゲン原子またはニトロ基である。炭素原子数１〜６のアルキル基として、メチル基、エチル基、ｎ−プロピル基、ｓｅｃ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、ｉｓｏ−ブチル基、ｎ−ペンチル基、ｓｅｃ−ペンチル基、ｉｓｏ−ペンチル基、ｎ−ヘキシル基、ｓｅｃ−ヘキシル基、ｉｓｏ−ヘキシル基等が挙げられる。また、ハロゲン原子として、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
化合物（Ａ）として、ｏ−クロロニトロベンゼン、ｏ−フロロニトロベンゼン、ｏ−ジニトロベンゼンが好適に使用される。これらは置換されていても良い。
化合物（Ａ）の量は、化合物（Ｂ）に対して、好ましくは４〜８当量、さらに好ましくは４〜６当量である。
In formula (A), R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X is a halogen atom or a nitro group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, sec-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group and iso-butyl. Group, n-pentyl group, sec-pentyl group, iso-pentyl group, n-hexyl group, sec-hexyl group, iso-hexyl group and the like. Moreover, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom.
As the compound (A), o-chloronitrobenzene, o-fluoronitrobenzene, and o-dinitrobenzene are preferably used. These may be substituted.
The amount of compound (A) is preferably 4-8 equivalents, more preferably 4-6 equivalents, relative to compound (B).
（化合物（Ｂ））
化合物（Ｂ）は下記式にて示される、ペンタエリスリトールである。
(Compound (B))
Compound (B) is pentaerythritol represented by the following formula.
（ニトロ体）
ニトロ体は下記式（Ｃ）で表される。
(Nitro body)
The nitro form is represented by the following formula (C).
式（Ｃ）中、Ｒは式（Ａ）と同じであり、水素原子または炭素原子数１〜６のアルキル基である。炭素原子数１〜６のアルキル基として、メチル基、エチル基、ｎ−プロピル基、ｓｅｃ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、ｉｓｏ−ブチル基、ｎ−ペンチル基、ｓｅｃ−ペンチル基、ｉｓｏ−ペンチル基、ｎ−ヘキシル基、ｓｅｃ−ヘキシル基、ｉｓｏ−ヘキシル基等が挙げられる。 In the formula (C), R is the same as in the formula (A) and is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, sec-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group and iso-butyl. Group, n-pentyl group, sec-pentyl group, iso-pentyl group, n-hexyl group, sec-hexyl group, iso-hexyl group and the like.
（相間移動触媒）
本発明において特徴的なことは、相間移動触媒およびアルカリ金属水酸化物の水溶液の存在下で、上記化合物（Ａ）と化合物（Ｂ）とを反応させることにある。
本発明において相間移動触媒は、下記式（ｉ）で表される化合物であることが好ましい。
(Phase transfer catalyst)
What is characteristic in the present invention is that the compound (A) and the compound (B) are reacted in the presence of a phase transfer catalyst and an aqueous solution of an alkali metal hydroxide.
In the present invention, the phase transfer catalyst is preferably a compound represented by the following formula (i).
式（ｉ）中、Ｒ１〜Ｒ４各々独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基から選ばれる基である。Ａ−はハロゲンアニオンである。 In formula (i), R1 to R4 are each independently a group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. A − is a halogen anion.
炭素原子数１〜２０のアルキル基として、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、へキサデシル基、オクタデシル基、ノナデシル基等が挙げられる。炭素原子数６〜２０のアリール基として、フェニル基、ナフチル基等が挙げられる。これらは、炭素原子数１〜１０のアルキル基で置換されていても良い。置換基としての炭素原子数１〜１０のアルキル基として、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等が挙げられる。炭素原子数７〜２０のアラルキル基として、ベンジル基、フェネチル基、メチルベンジル基、ジフェニルメチル基等が挙げられる。Ａ−のハロゲンアニオンとして、フッソイオン、塩素イオン、臭素イオン等が挙げられる。 Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, an octadecyl group, and a nonadecyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group. These may be substituted with an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms as a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, methylbenzyl group and diphenylmethyl group. Examples of the halogen anion for A − include a fluorine ion, a chlorine ion, and a bromine ion.
相間移動触媒として、テトラエチルアンモニウム塩、テトラブチルアンモニウム塩、トリオクチルメチルアンモニウム塩、ベンジルジメチルオクタデシルアンモニウム塩、ベンジルトリエチルアンモニウム塩、ベンジルトリメチルアンモニウム塩、ベンジルトリブチルアンモニウム塩を挙げることができ、これらは単独で用いても二種以上を併用してもよい。相間移動触媒として４級アンモニウム塩等が適用可能である。化合物（Ｂ）に対して、０．１〜５当量が使用可能である。 Examples of the phase transfer catalyst include tetraethylammonium salt, tetrabutylammonium salt, trioctylmethylammonium salt, benzyldimethyloctadecylammonium salt, benzyltriethylammonium salt, benzyltrimethylammonium salt, and benzyltributylammonium salt. Two or more types may be used in combination. A quaternary ammonium salt or the like is applicable as a phase transfer catalyst. 0.1-5 equivalent can be used with respect to a compound (B).
（アルカリ金属水酸化物の水溶液）
アルカリ金属として、ナトリウム、カリウム等が挙げられる。アルカリ金属水酸化物の水溶液としては、水酸化ナトリウム水溶液、水酸化カリウム水溶液が好ましく用いることができる。水溶液の濃度は、好ましくは６０〜２０重量パーセント、より好ましくは工業的に入手可能な４８〜３０重量パーセントである。
アルカリ金属水酸化物の水溶液として、水酸化ナトリウム水溶液または水酸化カリウム水溶液が好ましい。アルカリ金属水酸化物の水溶液は、連続に添加しても、分割に添加してもよい。アルカリ金属水酸化物の水溶液の使用量は、アルカリ金属水酸化物として、化合物（Ｂ）に対して４〜１５当量の範囲、反応の進行および経済性を考慮すると４．５〜１０当量が好ましい。
アルカリ金属水酸化物の水溶液は、炭酸カリウム、水素化ナトリウム、水酸化ナトリウム、水酸化カリウム等の固体塩基性化合物に比べ取り扱い易く、安価であるという利点を有する。
(Alkali metal hydroxide aqueous solution)
Examples of the alkali metal include sodium and potassium. As the aqueous solution of the alkali metal hydroxide, a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution can be preferably used. The concentration of the aqueous solution is preferably 60 to 20 weight percent, more preferably 48 to 30 weight percent, which is commercially available.
As the aqueous solution of the alkali metal hydroxide, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is preferable. The aqueous solution of alkali metal hydroxide may be added continuously or divided. The amount of the alkali metal hydroxide aqueous solution used is preferably 4 to 10 equivalents as the alkali metal hydroxide in consideration of the range of 4 to 15 equivalents, the progress of the reaction and the economy. .
An aqueous solution of an alkali metal hydroxide is advantageous in that it is easy to handle and inexpensive compared to solid basic compounds such as potassium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide and the like.
（反応）
反応系には、化合物（Ａ）の昇華性および融点の観点から、少量の有機溶媒を反応系に添加することもできるが、無論無溶媒でも実行可能である。反応終了後、反応液は強アルカリ性を示すが、酸で中和することも可能だが、しなくともよい。ろ過後の洗浄は、水溶性の不純物を洗い流すために水で洗浄することが好ましい。その後、原料等の不純物を洗い流すために有機溶媒で洗浄することができ、特に工業的に多用されているトルエンやメタノールが利用できる。またこれら有機溶媒は回収し、生産系へ戻すことが可能である。本反応系は高価な非プロトン性極性溶媒を使用しないため、当然その回収を必要とせず、工業的に有利に製造することができる。
(reaction)
A small amount of an organic solvent can be added to the reaction system from the viewpoint of the sublimability and melting point of the compound (A). After completion of the reaction, the reaction solution shows strong alkalinity, but it can be neutralized with an acid, but it is not necessary. Washing after filtration is preferably performed with water in order to wash away water-soluble impurities. Then, in order to wash away impurities, such as a raw material, it can wash | clean with an organic solvent, and especially toluene and methanol which are frequently used industrially can be utilized. These organic solvents can be recovered and returned to the production system. Since this reaction system does not use an expensive aprotic polar solvent, it naturally does not require recovery and can be produced industrially advantageously.
以下本発明を実施例によりさらに具体的に説明する。各値は以下の方法により求めた。 Hereinafter, the present invention will be described more specifically with reference to examples. Each value was determined by the following method.
（１）化合物の同定：
各化合物の同定は、ＮＭＲ：日本電子（株）製ＪＮＲ-ＥＸ２７０および質量分析計：（株）島津製作所製ＧＣＭＳ―ＱＰ５０００で行なった。
（２）収量、収率:
合成したニトロ体の収量、収率は、化合物（Ｂ）を基準として算出した。
（３）ＬＣ純度：
ＬＣ純度は、高速液体クロマトグラフィーを用いた分析により確認し、溶媒および原料化合物（Ａ）を除く各ピークの総面積値を１００としたときの、化合物（Ｃ）の面積パーセントを示す。
（４）選択率：
選択率とは、テトラニトロ体の面積値／（テトラニトロ体の面積値＋トリニトロモノハロゲン体の面積値）×1００で示される。
なお、テトラニトロ体およびトリニトロモノハロゲン体の面積値は高速液体クロマトグラフィーを用いた分析により求めた。
(1) Identification of compound:
Each compound was identified by NMR: JNR-EX270 manufactured by JEOL Ltd. and mass spectrometer: GCMS-QP5000 manufactured by Shimadzu Corporation.
(2) Yield, yield:
The yield and yield of the synthesized nitro compound were calculated based on the compound (B).
(3) LC purity:
The LC purity is confirmed by analysis using high performance liquid chromatography, and indicates the area percentage of the compound (C) when the total area value of each peak excluding the solvent and the raw material compound (A) is 100.
(4) Selectivity:
The selectivity is represented by the area value of tetranitro body / (area value of tetranitro body + area value of trinitromonohalogen body) × 100.
The area values of the tetranitro body and trinitromonohalogen body were determined by analysis using high performance liquid chromatography.
［実施例１］
ペンタエリスリトール：４．０８ｇ、ｏ−クロロニトロベンゼン：２３．６３ｇ、トルエン：４ｍｌ、塩化ベンジルトリエチルアンモニウム：６．８３ｇをガラス製反応機に仕込み、７０〜８５℃で４８％水酸化カリウム水溶液：３１．５６ｇを５時間かけ添加した。その後、同温度で２０時間反応させた。冷却後、水５０ｇを添加し、塩酸で中和した。その後ろ過し、水６０ｇ、メタノール９０ｍｌで順次洗浄後、乾燥し化合物（Ｃ）を得た（収量：１７．９０ｇ／収率：９６．２％／ＬＣ純度：９６．７％／選択率：９７．７％）。
[Example 1]
Pentaerythritol: 4.08 g, o-chloronitrobenzene: 23.63 g, toluene: 4 ml, benzyltriethylammonium chloride: 6.83 g were charged into a glass reactor, and a 48% potassium hydroxide aqueous solution: 31.70 at 70 to 85 ° C. 56 g was added over 5 hours. Then, it was made to react at the same temperature for 20 hours. After cooling, 50 g of water was added and neutralized with hydrochloric acid. Thereafter, the mixture was filtered, washed successively with 60 g of water and 90 ml of methanol, and dried to obtain compound (C) (yield: 17.90 g / yield: 96.2% / LC purity: 96.7% / selectivity: 97). .7%).
［実施例２］
ペンタエリスリトール：４．０８ｇ、ｏ−クロロニトロベンゼン：２３．６３ｇ、トルエン：４ｍｌ、水４．５ｇ、臭化テトラブチルアンモニウム：６．９６ｇをガラス製反応機に仕込み、８０〜８４℃で４８％水酸化ナトリウム水溶液：２２．５ｇを４時間４０分かけ添加した。その後、同温度で２２時間反応させた。冷却後、水：４０ｇ、トルエン：４ｍｌを添加し、塩酸で中和した。その後、ろ過し、水４０ｇ、メタノール６０ｍｌで順次洗浄後、乾燥し化合物（Ｃ）を得た（収量：１７．８９ｇ／収率：９６．１％／ＬＣ純度：９５．９％／選択率：９６．４％）。
[Example 2]
Pentaerythritol: 4.08 g, o-chloronitrobenzene: 23.63 g, toluene: 4 ml, water 4.5 g, tetrabutylammonium bromide: 6.96 g were charged into a glass reactor, and water was 48% at 80 to 84 ° C. Aqueous sodium oxide solution: 22.5 g was added over 4 hours and 40 minutes. Then, it was made to react at the same temperature for 22 hours. After cooling, 40 g of water and 4 ml of toluene were added and neutralized with hydrochloric acid. Thereafter, the mixture was filtered, washed successively with 40 g of water and 60 ml of methanol and dried to obtain compound (C) (yield: 17.89 g / yield: 96.1% / LC purity: 95.9% / selectivity: 96.4%).
［実施例３］
ペンタエリスリトール：１．３６ｇ、ｏ−フロロニトロベンゼン：６．７７ｇ、トルエン：２．５ｍｌ、臭化テトラブチルアンモニウム：０．７７ｇ、４８％水酸化カリウム：９．３５ｇをガラス製反応機に仕込み、７０℃で１８時間反応させた。冷却後濃塩酸で中和し、トルエン：７．５ｍｌを添加した。その後ろ過し、水：２０ｍｌ、メタノール：６０ｍｌで洗浄後、乾燥し化合物（Ｃ）を得た（収量：６．１８ｇ／収率：９９．６％／ＬＣ純度：９９．９％／選択率：１００％）。
[Example 3]
Pentaerythritol: 1.36 g, o-fluoronitrobenzene: 6.77 g, toluene: 2.5 ml, tetrabutylammonium bromide: 0.77 g, 48% potassium hydroxide: 9.35 g were charged into a glass reactor, 70 The reaction was carried out at 0 ° C. for 18 hours. After cooling, the mixture was neutralized with concentrated hydrochloric acid, and 7.5 ml of toluene was added. Thereafter, the mixture was filtered, washed with water: 20 ml, methanol: 60 ml and dried to obtain compound (C) (yield: 6.18 g / yield: 99.6% / LC purity: 99.9% / selectivity: 100%).
［実施例４］
ペンタエリスリトール：０．６８ｇ、ｏ−ジニトロベンゼン：４．２０ｇ、トルエン：３ｍｌ、臭化テトラブチルアンモニウム：０．３８ｇ、４８％水酸化ナトリウム：３．３３ｇをガラス製反応機に仕込み、５５℃で２０時間反応させた。冷却後、水：１０ｇを添加し濃塩酸で中和した。その後ろ過し、水：２０ｍｌ、メタノール：３０ｍｌで洗浄後、乾燥し化合物（Ｃ）を得た（収量：２．８０ｇ／収率：９０．２％／ＬＣ純度：９９．８％）。
[Example 4]
Pentaerythritol: 0.68 g, o-dinitrobenzene: 4.20 g, toluene: 3 ml, tetrabutylammonium bromide: 0.38 g, 48% sodium hydroxide: 3.33 g were charged into a glass reactor at 55 ° C. The reaction was performed for 20 hours. After cooling, 10 g of water was added and neutralized with concentrated hydrochloric acid. Thereafter, the mixture was filtered, washed with 20 ml of water and 30 ml of methanol, and dried to obtain compound (C) (yield: 2.80 g / yield: 90.2% / LC purity: 99.8%).
［参考例］（相間移動触媒未添加）
ペンタエリスリトール：０．６８ｇ、ｏ−クロロニトロベンゼン：３．９４ｇ、トルエン：５ｍｌ、３０％水酸化ナトリウム４．０ｇをガラス製反応機に仕込み、還流下２４時間反応させた。目的とする化合物（Ｃ）は、全く得られなかった。
[Reference Example] (No phase transfer catalyst added)
Pentaerythritol: 0.68 g, o-chloronitrobenzene: 3.94 g, toluene: 5 ml, 30% sodium hydroxide 4.0 g were charged into a glass reactor and reacted under reflux for 24 hours. The target compound (C) was not obtained at all.
［比較例］
ペンタエリスリトール：１．３６ｇ、ｏ−クロロニトロベンゼン：６．６１ｇ、Ｎ，Ｎ−ジメチルアセトアミド：１３ｇ、固体水酸化ナトリウム２．０ｇをガラス製反応機に仕込み、６０℃で２３時間反応させた。冷却後、水２０ｇを添加し、上澄み液を廃棄後、メタノール３０ｍｌを添加し、結晶を分散させた。ろ過後、水３０ｍｌ、メタノール３０ｍｌで洗浄し、乾燥後化合物（Ｃ）を得た（収量：４．５１ｇ／収率：７２．７％／ＬＣ純度：７７．４％／選択率：９５．２％）。
[Comparative example]
Pentaerythritol: 1.36 g, o-chloronitrobenzene: 6.61 g, N, N-dimethylacetamide: 13 g, and 2.0 g of solid sodium hydroxide were charged into a glass reactor and reacted at 60 ° C. for 23 hours. After cooling, 20 g of water was added, the supernatant was discarded, and 30 ml of methanol was added to disperse the crystals. After filtration, the product was washed with 30 ml of water and 30 ml of methanol, and dried to obtain compound (C) (yield: 4.51 g / yield: 72.7% / LC purity: 77.4% / selectivity: 95.2). %).
本発明で得られる式（Ｃ）で表されるニトロ体は、ポリエステルの末端封止剤として有用な環状カルボジイミド化合物の中間体である。
The nitro body represented by the formula (C) obtained in the present invention is an intermediate of a cyclic carbodiimide compound that is useful as an end-capping agent for polyester.
Claims (4)
The method according to claim 1, wherein the aqueous solution of the alkali metal hydroxide is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution.
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| JP2010137173A JP5560109B2 (en) | 2010-06-16 | 2010-06-16 | Method for producing nitro compound |
| US13/704,117 US9428521B2 (en) | 2010-06-16 | 2011-06-15 | Process for the production of a carbodiimide |
| CN201180029335.0A CN103025743B (en) | 2010-06-16 | 2011-06-15 | The manufacture method of carbon imide compound |
| EP11795860.3A EP2583971B1 (en) | 2010-06-16 | 2011-06-15 | Method for producing carbodiimide |
| PCT/JP2011/064193 WO2011158958A1 (en) | 2010-06-16 | 2011-06-15 | Method for producing carbodiimide |
| TW100120878A TWI486351B (en) | 2010-06-16 | 2011-06-15 | Production method of carbon imide body |
| KR1020127032612A KR20130129822A (en) | 2010-06-16 | 2011-06-15 | Method for producing carbodiimide |
| ES11795860.3T ES2538090T3 (en) | 2010-06-16 | 2011-06-15 | Process for the production of a carbodiimide |
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| JP2012001476A (en) * | 2010-06-16 | 2012-01-05 | Kawaguchi Kagaku Kogyo Kk | Method for producing carbodiimide compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6429349A (en) * | 1987-07-08 | 1989-01-31 | Bayer Ag | Aromatic polyisocyanates, preparation and use as component for adhesive |
| JPH0499755A (en) * | 1990-08-15 | 1992-03-31 | Honsyu Kagaku Kogyo Kk | Production of 1,3-dinitro-4-(2',2',2'-trifluoroethoxy)benzene |
| WO2010071211A1 (en) * | 2008-12-15 | 2010-06-24 | 帝人株式会社 | Cyclic carbodiimide compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6429349A (en) * | 1987-07-08 | 1989-01-31 | Bayer Ag | Aromatic polyisocyanates, preparation and use as component for adhesive |
| JPH0499755A (en) * | 1990-08-15 | 1992-03-31 | Honsyu Kagaku Kogyo Kk | Production of 1,3-dinitro-4-(2',2',2'-trifluoroethoxy)benzene |
| WO2010071211A1 (en) * | 2008-12-15 | 2010-06-24 | 帝人株式会社 | Cyclic carbodiimide compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012001476A (en) * | 2010-06-16 | 2012-01-05 | Kawaguchi Kagaku Kogyo Kk | Method for producing carbodiimide compound |
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