JP4314366B2 - Method for producing phosphorus-containing butadiene compound - Google Patents
Method for producing phosphorus-containing butadiene compound Download PDFInfo
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- JP4314366B2 JP4314366B2 JP2004042139A JP2004042139A JP4314366B2 JP 4314366 B2 JP4314366 B2 JP 4314366B2 JP 2004042139 A JP2004042139 A JP 2004042139A JP 2004042139 A JP2004042139 A JP 2004042139A JP 4314366 B2 JP4314366 B2 JP 4314366B2
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- -1 butadiene compound Chemical class 0.000 title claims description 34
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 14
- 239000011574 phosphorus Substances 0.000 title claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000004104 aryloxy group Chemical group 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 description 2
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 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 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000000524 functional group Chemical group 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
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003003 phosphines Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- FQDIANVAWVHZIR-UHFFFAOYSA-N 1,4-dichlorobut-2-ene Chemical compound ClCC=CCCl FQDIANVAWVHZIR-UHFFFAOYSA-N 0.000 description 1
- UIGLAZDLBZDVBL-UHFFFAOYSA-N 1-phenylprop-2-yn-1-ol Chemical compound C#CC(O)C1=CC=CC=C1 UIGLAZDLBZDVBL-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LAQYTBYMZXHCLC-UHFFFAOYSA-N [cyclohexyloxy(oxido)phosphaniumyl]benzene Chemical compound C=1C=CC=CC=1P(=O)OC1CCCCC1 LAQYTBYMZXHCLC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- IQUAECJNIZFLIC-UHFFFAOYSA-N benzhydrylphosphane nickel Chemical compound [Ni].PC(C1=CC=CC=C1)C1=CC=CC=C1.PC(C1=CC=CC=C1)C1=CC=CC=C1.PC(C1=CC=CC=C1)C1=CC=CC=C1.PC(C1=CC=CC=C1)C1=CC=CC=C1 IQUAECJNIZFLIC-UHFFFAOYSA-N 0.000 description 1
- WBMDPNTUYFBKNY-UHFFFAOYSA-N benzhydrylphosphane nickel Chemical compound [Ni].C1(=CC=CC=C1)C(C1=CC=CC=C1)P WBMDPNTUYFBKNY-UHFFFAOYSA-N 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
- GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 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 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- OSPSWZSRKYCQPF-UHFFFAOYSA-N dibutoxy(oxo)phosphanium Chemical compound CCCCO[P+](=O)OCCCC OSPSWZSRKYCQPF-UHFFFAOYSA-N 0.000 description 1
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- JZUYMDPYNGVRSD-UHFFFAOYSA-N dimethyl(phenyl)phosphane nickel Chemical compound [Ni].CP(C1=CC=CC=C1)C JZUYMDPYNGVRSD-UHFFFAOYSA-N 0.000 description 1
- UJNLHRZSJZQQOB-UHFFFAOYSA-N dimethyl(phenyl)phosphane;nickel Chemical compound [Ni].CP(C)C1=CC=CC=C1.CP(C)C1=CC=CC=C1.CP(C)C1=CC=CC=C1.CP(C)C1=CC=CC=C1 UJNLHRZSJZQQOB-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- GOJNABIZVJCYFL-UHFFFAOYSA-N dimethylphosphinic acid Chemical compound CP(C)(O)=O GOJNABIZVJCYFL-UHFFFAOYSA-N 0.000 description 1
- BEQVQKJCLJBTKZ-UHFFFAOYSA-N diphenylphosphinic acid Chemical compound C=1C=CC=CC=1P(=O)(O)C1=CC=CC=C1 BEQVQKJCLJBTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- YJSXLGKPMXKZJR-UHFFFAOYSA-N ethoxy-oxo-phenylphosphanium Chemical compound CCO[P+](=O)C1=CC=CC=C1 YJSXLGKPMXKZJR-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- WEGVIDVCQHPAKB-UHFFFAOYSA-N nickel;triethylphosphane Chemical compound [Ni].CCP(CC)CC.CCP(CC)CC.CCP(CC)CC.CCP(CC)CC WEGVIDVCQHPAKB-UHFFFAOYSA-N 0.000 description 1
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 description 1
- QCYXGORGJYUYMT-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QCYXGORGJYUYMT-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006187 phenyl benzyl group Chemical group 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Description
本発明は、ブタジエンと同様、反応性に富んでおり、容易に重合し、機能性高分子を与える、含リンブタジエン化合物の新規な製造方法に関するものである。 The present invention relates to a novel method for producing a phosphorus-containing butadiene compound that is highly reactive and, like butadiene, easily polymerizes to give a functional polymer.
含リンブタジエン化合物は、従来公知の化合物であり、たとえば以下の置換反応により製造されている。
(1)リンハライドCH2CH-CH=CHP(O)Cl2とグリニャールや有機リチウム試薬との反応
(2)MeCH=C=C(Me)[CMe2(OH)]とリンハライドPh2PClとの反応
(3)(EtO)3PとClCH2CH=CHCH2Clとの反応
しかし、これらの方法は、毒性のあるハライド類を用いる必要があり、また、反応に伴って同時に大量の塩やハライドガス類が発生するため、工業的に有利な方法ではなかった。
The phosphorus-containing butadiene compound is a conventionally known compound and is produced, for example, by the following substitution reaction.
(1) Reaction of phosphorus halide CH 2 CH—CH═CHP (O) Cl 2 with Grignard or organolithium reagent (2) MeCH = C = C (Me) [CMe 2 (OH)] and phosphorus halide Ph 2 PCl Reaction (3) Reaction of (EtO) 3 P with ClCH 2 CH═CHCH 2 Cl However, these methods require the use of toxic halides, and at the same time, a large amount of salts and halides are accompanied with the reaction. Since gases are generated, it is not an industrially advantageous method.
本発明は、毒性のあるハライド類を使用することなく、安全かつ簡便で高選択的に製造し得る工業的に有利な含リン置換ブタジエン化合物の製造方法を提供することを目的とする。 An object of the present invention is to provide an industrially advantageous method for producing a phosphorus-containing substituted butadiene compound that can be produced safely, simply and highly selectively without using toxic halides.
本発明者等は、リン水素化物とプロパルギルアセチレン化合物の反応性を鋭意検討する過程で、含リンブタジエン化合物が容易に生成することを見出し、かかる知見に基づいて本発明を完成するに至った。 The present inventors have found that a phosphorus-containing butadiene compound is easily formed in the process of intensively examining the reactivity between a phosphorus hydride and a propargyl acetylene compound, and have completed the present invention based on such knowledge.
すなわち、この出願によれば、以下の発明が提供される。
〈1〉
下記一般式(1)
X1X2P(O)H (1)
(X1、X2は、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基又はアリールオキシ基を示す。)
で表されるリン水素化合物と、下記一般式(2)
R1(R2R3CH)C(OH)C≡CR4 (2)
(R1、R2、R3、R4は水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基、アリールオキシ基又はシリル基を示す。)
で表されるアセチレン化合物を、ニッケルを含む触媒と下記一般式(5)
HO−P(O)(R5)2 (5)
(式中、R5はアルキル基、シクロアルキル基またはアリール基を示す。)
で表されるホスフィン酸の存在下で、反応させることを特徴とする下記一般式(3)
R2R3C=C(R1)-CH=CR4[P(O)X1X2] (3)
及び/または、下記一般式(4)
R2R3C=C(R1)-C[P(O)X1X2]=CR4H (4)
(R1、R2、R3、R4、X1、X2は、前記と同じ)
で表される含リンブタジエン化合物の製造方法。
That is, according to this application, the following invention is provided.
<1>
The following general formula (1)
X 1 X 2 P (O) H (1)
(X 1 and X 2 represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group or an aryloxy group.)
A phosphorus hydrogen compound represented by the following general formula (2)
R 1 (R 2 R 3 CH) C (OH) C≡CR 4 (2)
(R 1 , R 2 , R 3 and R 4 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, an aryloxy group or a silyl group.)
An acetylene compound represented by the formula: (5)
HO-P (O) (R 5) 2 (5)
(In the formula, R 5 represents an alkyl group, a cycloalkyl group or an aryl group.)
The reaction is carried out in the presence of phosphinic acid represented by the following general formula (3)
R 2 R 3 C = C (R 1 ) -CH = CR 4 [P (O) X 1 X 2 ] (3)
And / or the following general formula (4)
R 2 R 3 C = C (R 1 ) -C [P (O) X 1 X 2 ] = CR 4 H (4)
(R 1 , R 2 , R 3 , R 4 , X 1 , X 2 are the same as above)
The manufacturing method of the phosphorus-containing butadiene compound represented by these.
本発明の合成方法は、アセチレン化合物とリン水素化物を直接反応させるという、簡便かつ安全な手段により、含リンブタジエン化合物を高選択的に合成することができ、生成物の分離精製も容易である。従って、本発明は工業的に有用である。 According to the synthesis method of the present invention, a phosphorus-containing butadiene compound can be synthesized with high selectivity by a simple and safe means of directly reacting an acetylene compound and a phosphorus hydride, and separation and purification of the product is easy. . Therefore, the present invention is industrially useful.
本発明においては、前記一般式(1)で表されるリン水素化合物と前記一般式(2)で表されるアセチレン化合物と直接接触させ、脱水、付加反応させることにより、前記一般式(3)及び/または(4)で示される含リンブタジエン化合物を合成する。 In the present invention, the phosphorus hydrogen compound represented by the general formula (1) and the acetylene compound represented by the general formula (2) are brought into direct contact, followed by dehydration and addition reaction, whereby the general formula (3) And / or the phosphorus-containing butadiene compound represented by (4) is synthesized.
前記一般式(1)において、X1、X2は、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基又はアリールオキシ基を示すが、これらの例としては、後記するR1〜R4はと同様なものが挙げられる。 In the general formula (1), X 1 and X 2 each represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, or an aryloxy group. , R 1 to R 4 described later are the same as those described above.
また、前記一般式(2)乃至(4)において、R1〜R4は、水素原子、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基又はアリールオキシ基を示す。 In the general formulas (2) to (4), R 1 to R 4 are each a hydrogen atom, a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group, or An aryloxy group is shown.
アルキル基の場合のアルキル基の炭素数は1〜18、好ましくは1〜10である。その具体例としては、メチル基、エチル基、プロピル基、ヘキシル基、デシル基などが挙げられる。 In the case of an alkyl group, the alkyl group has 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a hexyl group, and a decyl group.
シクロアルキル基の場合の炭素数は5〜18、好ましくは5〜12である。その具体例としては、シクロヘキシル基、シクロオクチル基、シクロドデシル基などが挙げられる。 In the case of a cycloalkyl group, the carbon number is 5-18, preferably 5-12. Specific examples thereof include a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group.
アリール基の場合の炭素数は6〜14、好ましくは6〜10である。その具体例としては、フェニル基、ナフチル基が挙げられ、さらにそれらの置換体(トリル基、キシリル基、ベンジルフェニル基など)も包含される。 In the case of an aryl group, the number of carbon atoms is 6 to 14, preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group, and further include substitutions thereof (tolyl group, xylyl group, benzylphenyl group, etc.).
ヘテロアリール基の場合のヘテロアリール基は、酸素、窒素、イオウなどのヘテロ原子を含む各種の複素芳香環基であり、それに含まれる炭素数は4〜12、好ましくは4〜8である。その具体例としては、チエニル基、フリル基、ピリジル基、ピロリル基などが挙げられる。 The heteroaryl group in the case of a heteroaryl group is various heteroaromatic ring groups containing hetero atoms, such as oxygen, nitrogen, and sulfur, The carbon number contained in it is 4-12, Preferably it is 4-8. Specific examples thereof include a thienyl group, a furyl group, a pyridyl group, and a pyrrolyl group.
アラルキル基の場合の炭素数は7〜13、好ましくは7〜9である。その具体例としては、ベンジル基、フェネチル基、フェニルベンジル基、ナフチルメチル基などが挙げられる。 In the case of an aralkyl group, the carbon number is 7 to 13, preferably 7 to 9. Specific examples thereof include a benzyl group, a phenethyl group, a phenylbenzyl group, and a naphthylmethyl group.
アルケニル基の場合の炭素数は2〜18、好ましくは2〜10である。その具体例として、ビニル基、3−ブテニル基、シクロヘキセニル基などが挙げられる。 In the case of an alkenyl group, the carbon number is 2-18, preferably 2-10. Specific examples thereof include a vinyl group, a 3-butenyl group, and a cyclohexenyl group.
アルコキシ基の場合の炭素数は1〜8、好ましくは1〜4である。その具体例としては、メトキシ基、エトキシ基、ブトキシ基などが挙げられる。 The number of carbon atoms in the case of an alkoxy group is 1-8, preferably 1-4. Specific examples thereof include a methoxy group, an ethoxy group, and a butoxy group.
アリールオキシ基の場合の炭素数は6〜14、好ましくは6〜10である。その具体例としては、フェノキシ基、ナフトキシ基などが挙げられる。シリル基の場合には、アルキル基やアリール基、アラルキル基、アルコキシ基で置換されたものが含まれる。その具体例として、トリメチルシリル基、トリエチルシリル基、トリフェニルシリル基、フェニルジメチルシリル基、トリメトキシシリル基、t-ブチルジメチルシリル基などが挙げられる。 In the case of an aryloxy group, the carbon number is 6 to 14, preferably 6 to 10. Specific examples thereof include a phenoxy group and a naphthoxy group. In the case of a silyl group, those substituted with an alkyl group, an aryl group, an aralkyl group, or an alkoxy group are included. Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a phenyldimethylsilyl group, a trimethoxysilyl group, and a t-butyldimethylsilyl group.
また、R1〜R4は、反応に不活性な官能基、例えば、メトキシ基、メトキシカルボニル基、シアノ基、ジメチルアミノ基、フルオロ基、クロロ基、ヒドロキシ基などで置換されていてもよい。 R 1 to R 4 may be substituted with a functional group inert to the reaction, such as a methoxy group, a methoxycarbonyl group, a cyano group, a dimethylamino group, a fluoro group, a chloro group, or a hydroxy group.
前記一般式(1)で表される好適なリン水素化物を具体的に例示すると、ジメチルホスホン酸エステル、ジエチルホスホン酸エステル、ジブチルホスホン酸エステル、ジフェニルホスホン酸エステル、4,4,5,5-テトラメチル−1,3,2−ジオキサホスホラン2−オキシド、フェニルホスフィン酸エチル、フェニルホスフィン酸シクロヘキシル、ジフェニルホスフィンオキシドなどが挙げられるが、これらに限定されるものではない。 Specific examples of suitable phosphorus hydrides represented by the general formula (1) include dimethylphosphonate, diethylphosphonate, dibutylphosphonate, diphenylphosphonate, 4,4,5,5- Examples thereof include, but are not limited to, tetramethyl-1,3,2-dioxaphosphorane 2-oxide, ethyl phenylphosphinate, cyclohexyl phenylphosphinate, and diphenylphosphine oxide.
また、前記一般式(2)で示されるアセチレン化合物を例示すると、1−ブチンー3−オル、2−メチル−3−ブチン−2−オル、1−エチニル−1−シクロヘキサノール、1−ヘキシン−3−オル、1−フェニル-2-プロピン−1−オルなどが挙げられるが、これらに限定されるものではない。 Examples of the acetylene compound represented by the general formula (2) include 1-butyn-3-ol, 2-methyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, and 1-hexyne-3. -Ol, 1-phenyl-2-propyn-1-ol and the like, but are not limited thereto.
前記アセチレン化合物と前記リン水素化物の使用比率は、一般的にモル比で1:1が好ましいが、これより大きくても小さくても、反応の生起を阻害するものではない。 The molar ratio of the acetylene compound and the phosphorus hydride used is generally preferably 1: 1, but it does not hinder the occurrence of the reaction even if it is larger or smaller than this.
本発明の反応を効率よく生起させるには、低原子価のニッケル触媒の使用が好ましい。その形態としては、種々の構造のものを用いることができるが、好適なものは3級ホスフィンを配位子とするものが特に好ましい。また、反応系中で容易に低原子価に変換される前駆体を用いることも好ましい態様である。さらに、反応系中で、3級ホスフィンを配位子として含まない錯体と3級ホスフィンを混合し、反応系中で3級ホスフィンを配位子とする錯体を発生する方法も好ましい態様である。これらのいずれかの方法で有利な性能を発揮する配位子としては、種々の3級ホスフィンが挙げられる。 In order to efficiently cause the reaction of the present invention, it is preferable to use a low-valence nickel catalyst. Although the thing of various structures can be used as the form, The thing which has tertiary phosphine as a ligand is especially preferable. It is also a preferred embodiment to use a precursor that is easily converted to a low valence in the reaction system. Further, a method in which a complex containing no tertiary phosphine as a ligand and a tertiary phosphine are mixed in the reaction system to generate a complex having the tertiary phosphine as a ligand in the reaction system is also a preferred embodiment. Examples of the ligand that exhibits advantageous performance by any of these methods include various tertiary phosphines.
本発明において、好適に用いることができる配位子を例示すると、トリフェニルホスフィン、ジフェニルメチルホスフィン、フェニルジメチルホスフィン、1,4−ビス(ジフェニルホスフィノ)ブタン、1,3−ビス(ジフェニルホスフィノ)プロパン、1,2−ビス(ジフェニルホスフィノ)エタン、1,1'-ビス(ジフェニルホスフィノ)フェロセン、トリエチルホスフィン、トリメチルホスフィンなどが挙げられるが、これらに限定されたものではない。 Examples of ligands that can be preferably used in the present invention include triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,4-bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino). ), Propane, 1,2-bis (diphenylphosphino) ethane, 1,1′-bis (diphenylphosphino) ferrocene, triethylphosphine, trimethylphosphine, and the like, but are not limited thereto.
これに組み合わせてまたは単独で用いられる、3級ホスフィンを配位として含まない錯体としては、ビス(1,5−シクロオクタジエン)ニッケルなどが挙げられるが、これらに限定されるものではない。 Examples of the complex not containing tertiary phosphine as a coordination used in combination or alone include bis (1,5-cyclooctadiene) nickel, but are not limited thereto.
また、好適に用いられるホスフィン錯体の具体例としては、テトラキス(トリフェニルホスフィン)ニッケル、テトラキス(ジフェニルメチルホスフィン)ニッケル、テトラキス(ジメチルフェニルホスフィン)ニッケル、テトラキス(トリエチルホスフィン)ニッケルなどがあげられる。 Specific examples of phosphine complexes that can be suitably used include tetrakis (triphenylphosphine) nickel, tetrakis (diphenylmethylphosphine) nickel, tetrakis (dimethylphenylphosphine) nickel, tetrakis (triethylphosphine) nickel, and the like.
さらに、容易に低原子価に変換される前駆体を用い、反応系中でグリニャールや有機リチウムなどの有機金属試剤との反応により、容易に高活性ニッケル触媒を発生させることもできる。その前駆体の具体例として、ジクロロビス(トリフェニルホスフィン)ニッケル、ジクロロビス(ジフェニルメチルホスフィン)ニッケル、ジクロロビス(ジメチルフェニルホスフィン)ニッケルなどがあげられるが、これらに限定されたものではない。 Furthermore, a highly active nickel catalyst can be easily generated by reaction with an organometallic reagent such as Grignard or organolithium in a reaction system using a precursor that is easily converted to a low valence. Specific examples of the precursor include dichlorobis (triphenylphosphine) nickel, dichlorobis (diphenylmethylphosphine) nickel, dichlorobis (dimethylphenylphosphine) nickel and the like, but are not limited thereto.
これらの触媒の使用量はいわゆる触媒量でよく、一般的にアセチレン化合物に対して20モル%以下で十分である。 The amount of these catalysts used may be a so-called catalytic amount, and generally 20 mol% or less is sufficient with respect to the acetylene compound.
ニッケル触媒は、単独でも活性を示すが、ホスフィン酸添加剤と共に用いることも出来る。また、ホスフィン酸添加剤を用いることにより、生成物の選択性が改善されることができる。これらのホスフィン酸は、一般式(5)で表され、R5はアルキル基、シクロアルキル基またはアリール基を示す。 The nickel catalyst is active alone, but can also be used with a phosphinic acid additive. Moreover, the selectivity of a product can be improved by using a phosphinic acid additive. These phosphinic acids are represented by the general formula (5) , and R 5 represents an alkyl group, a cycloalkyl group or an aryl group.
R5がアルキル基の場合のアルキル基の炭素数は1〜6、好ましくは1〜4である。その具体例としては、メチル、エチル、プロピル、ヘキシルなどが挙げられる。前記シクロアルキル基の場合の炭素数は3〜12、好ましくは5〜6である。その具体例としては、シクロヘキシル基、シクロオクチル基、シクロドデシル基などが挙げられる。前記アリール基の場合の炭素数は6〜14、好ましくは6〜10である。その具体例としては、フェニル基、ナフチル基が挙げられ、さらにそれらの置換体(トリル基、キシリル基、ベンジルフェニル基など)も包含される。 When R 5 is an alkyl group, the alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, hexyl and the like. In the case of the said cycloalkyl group, carbon number is 3-12, Preferably it is 5-6. Specific examples thereof include a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group. The number of carbon atoms in the case of the aryl group is 6 to 14, preferably 6 to 10. Specific examples thereof include a phenyl group and a naphthyl group, and further include substitution products thereof (tolyl group, xylyl group, benzylphenyl group, etc.).
R5で示されるアルキル基、シクロアルキル基またはアリール基は,反応に不活性な官能基、例えば、メトキシ基、メトキシカルボニル基、シアノ基、ジメチルアミノ基、フルオロ基、クロロ基、ヒドロキシ基などで置換されていてもよい。 The alkyl group, cycloalkyl group or aryl group represented by R 5 is a functional group inert to the reaction, for example, a methoxy group, a methoxycarbonyl group, a cyano group, a dimethylamino group, a fluoro group, a chloro group, a hydroxy group and the like. May be substituted.
用いるホスフィン酸の具体例としては、ジフェニルホスフィン酸やジメチルホスフィン酸などが挙げられる。その使用量は、用いるP−H化合物に対して同モル以下、好ましくは、0.1〜10モル%である。 Specific examples of the phosphinic acid to be used include diphenylphosphinic acid and dimethylphosphinic acid. The amount used is equal to or less than that of the P—H compound to be used, preferably 0.1 to 10 mol%.
反応は特に溶媒を用いなくてもよいが、必要に応じて溶媒中で実施することもできる。溶媒としては、炭化水素類、ハロゲン炭化水素類、エーテル類、ケトン類、ニトリル類、エステル類など種々のものが使用できる。また、これらは単独若しくは2種以上の混合物として使用される。 The reaction is not particularly required to use a solvent, but can be carried out in a solvent if necessary. Various solvents such as hydrocarbons, halogen hydrocarbons, ethers, ketones, nitriles, and esters can be used as the solvent. Moreover, these are used individually or in mixture of 2 or more types.
反応温度は、あまりに低温では反応が有利な速度で進行せず、あまりに高温では触媒が分解するので、一般的には、零下20℃ないし150℃の範囲から選ばれ、好ましくは室温ないし100℃の範囲で実施される。 The reaction temperature is selected from the range of 20 ° C. to 150 ° C. below zero, preferably from room temperature to 100 ° C., because the reaction does not proceed at an advantageous rate at too low temperatures and the catalyst decomposes at too high temperatures. Implemented in a range.
本反応に用いられる触媒は、酸素に敏感であり、反応の実施は、窒素やアルゴン、メタン等の不活性ガス雰囲気で行うのが好ましい。反応混合物からの生成物の分離は、クロマトグラフィー、蒸留または再結晶によって容易に達成される。 The catalyst used in this reaction is sensitive to oxygen, and the reaction is preferably carried out in an inert gas atmosphere such as nitrogen, argon or methane. Separation of the product from the reaction mixture is readily accomplished by chromatography, distillation or recrystallization.
本発明を以下の実施例によってさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
実施例1
THF 1ミリリットルに、HP(O)Ph2 1 ミリモル、2−メチル−3−ブチン−2−オル 1ミリモル、触媒として Ni(PPhMe2)4(5 モル%)とPh2P(O)OH (5 モル%)を用い、窒素雰囲気下、室温で5時間反応させたところ、CH2=C(Me)CH=CH[P(O)Ph2]とCH2=C(Me)C[P(O)Ph2]=CH2が(比率=39:61)91%の収率で得られた。
Example 1
1 ml of THF, 1 mmol of HP (O) Ph 2, 1 mmol of 2-methyl-3-butyn-2-ol, Ni (PPhMe 2 ) 4 (5 mol%) and Ph 2 P (O) OH ( 5 mol%) and a reaction at room temperature in a nitrogen atmosphere for 5 hours. CH 2 = C (Me) CH = CH [P (O) Ph 2 ] and CH 2 = C (Me) C [P ( O) Ph 2 ] = CH 2 (ratio = 39: 61) was obtained with a yield of 91%.
実施例2
THFの代わりに、ベンゼンを用いた以外は実施例1と同様な条件下反応をおこなたっところ、CH2=C(Me)CH=CH[P(O)Ph2]とCH2=C(Me)C[P(O)Ph2]=CH2が(比率=22:78)87%の収率で得られた。
Example 2
The reaction was conducted under the same conditions as in Example 1 except that benzene was used instead of THF, and CH 2 = C (Me) CH = CH [P (O) Ph 2 ] and CH 2 = C ( Me) C [P (O) Ph 2 ] = CH 2 (ratio = 22: 78) was obtained in a yield of 87%.
実施例3
Ni(PPhMe2)4の代わりに、触媒として、Ni(cod)2(5 モル%) とPPhMe2 (5 モル%)を用い、実施例1の条件で反応を行った。CH2=C(Me)CH=CH[P(O)Ph2]とCH2=C(Me)C[P(O)Ph2]=CH2が(比率=17:83)73%の収率で得られた。
Example 3
Instead of Ni (PPhMe 2 ) 4 , Ni (cod) 2 (5 mol%) and PPhMe 2 (5 mol%) were used as catalysts, and the reaction was carried out under the conditions of Example 1. CH 2 = C (Me) CH = CH [P (O) Ph 2 ] and CH 2 = C (Me) C [P (O) Ph 2 ] = CH 2 (ratio = 17:83) Obtained at a rate.
実施例4
触媒として、Ni(cod)2(5 モル%) とPPhMe2 (10 モル%)を用い、実施例3の条件で反応を行った。CH2=C(Me)CH=CH[P(O)Ph2]とCH2=C(Me)C[P(O)Ph2]=CH2が(比率=31:69)92%の収率で得られた。
Example 4
The reaction was carried out under the conditions of Example 3 using Ni (cod) 2 (5 mol%) and PPhMe 2 (10 mol%) as catalysts. CH 2 = C (Me) CH = CH [P (O) Ph 2 ] and CH 2 = C (Me) C [P (O) Ph 2 ] = CH 2 (ratio = 31: 69) yield of 92% Obtained at a rate.
実施例5
触媒として、Ni(cod)2(5 モル%) とPPhMe2 (20 モル%)を用い、実施例3の条件で反応を行った。CH2=C(Me)CH=CH[P(O)Ph2]とCH2=C(Me)C[P(O)Ph2]=CH2が(比率=31:69)95%の収率で得られた。
Example 5
The reaction was carried out under the conditions of Example 3 using Ni (cod) 2 (5 mol%) and PPhMe 2 (20 mol%) as catalysts. CH 2 = C (Me) CH = CH [P (O) Ph 2 ] and CH 2 = C (Me) C [P (O) Ph 2 ] = CH 2 (ratio = 31: 69) yield of 95% Obtained at a rate.
実施例6
実施例1の条件下、1−エチニル−1−シクロヘキサノールを用いて反応を行った。(1-C6H9)CH=CH[P(O)Ph2]と(1-C6H9)[P(O)Ph2]C=CH2が(比率=41:59)92%の収率で得られた。
Example 6
The reaction was carried out using 1-ethynyl-1-cyclohexanol under the conditions of Example 1. (1-C 6 H 9 ) CH = CH [P (O) Ph 2 ] and (1-C 6 H 9 ) [P (O) Ph 2 ] C = CH 2 (ratio = 41: 59) 92% The yield was obtained.
実施例7
実施例1の条件下、Ph2P(O)Hの代わりに、(MeO)2P(O)H、また、Ni(PPhMe2)4の代わりにNi(PPh2Me)4を用いて反応を行った。CH2=C(Me)CH=CH[P(O)(OMe)2]とCH2=C(Me)C[P(O)(OMe)2]=CH2が(比率=77:23)76%の収率で得られた。
Example 7
Reaction under the conditions of Example 1 using (MeO) 2 P (O) H instead of Ph 2 P (O) H and Ni (PPh 2 Me) 4 instead of Ni (PPhMe 2 ) 4 Went. CH 2 = C (Me) CH = CH [P (O) (OMe) 2 ] and CH 2 = C (Me) C [P (O) (OMe) 2 ] = CH 2 (ratio = 77: 23) Obtained in a yield of 76%.
実施例8
実施例1の条件下、Ph2P(O)Hの代わりに、Ph(EtO)P(O)Hを用いて反応を行った。CH2=C(Me)CH=CH[P(O)Ph(OEt)]とCH2=C(Me)C[P(O)(OEt)Ph]=CH2が(比率=55:45)
87%の収率で得られた。
Example 8
Under the conditions of Example 1, the reaction was performed using Ph (EtO) P (O) H instead of Ph 2 P (O) H. CH 2 = C (Me) CH = CH [P (O) Ph (OEt)] and CH 2 = C (Me) C [P (O) (OEt) Ph] = CH 2 (ratio = 55: 45)
Obtained in a yield of 87%.
Claims (1)
X X 11 XX 22 P(O)H (1)P (O) H (1)
(X(X 11 、X, X 22 は、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基又はアリールオキシ基を示す。)Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a heteroaryl group, an alkenyl group, an alkoxy group or an aryloxy group. )
で表されるリン水素化合物と、下記一般式(2)A phosphorus hydrogen compound represented by the following general formula (2)
R R 11 (R(R 22 RR 3Three CH)C(OH)C≡CRCH) C (OH) C≡CR 4 Four (2)(2)
(R(R 11 、R, R 22 、R, R 3Three 、R, R 4Four は水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、ヘテロアリール基、アルケニル基、アルコキシ基、アリールオキシ基又はシリル基を示す。)Represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, heteroaryl group, alkenyl group, alkoxy group, aryloxy group or silyl group. )
で表されるアセチレン化合物を、ニッケルを含む触媒と下記一般式(5)An acetylene compound represented by the formula: (5)
HO−P(O)(R HO-P (O) (R 55 )) 22 (5)(5)
(式中、R(Where R 55 はアルキル基、シクロアルキル基またはアリール基を示す。)Represents an alkyl group, a cycloalkyl group or an aryl group. )
で表されるホスフィン酸の存在下で、反応させることを特徴とする下記一般式(3)The reaction is carried out in the presence of phosphinic acid represented by the following general formula (3)
R R 22 RR 3Three C=C(RC = C (R 11 )-CH=CR) -CH = CR 4Four [P(O)X[P (O) X 11 XX 22 ] (3)] (3)
及び/または、下記一般式(4)And / or the following general formula (4)
R R 22 RR 3Three C=C(RC = C (R 11 )-C[P(O)X) -C [P (O) X 11 XX 22 ]=CR] = CR 4Four H (4)H (4)
(R(R 11 、R, R 22 、R, R 3Three 、R, R 4Four 、X, X 11 、X, X 22 は、前記と同じ)Is the same as above)
で表される含リンブタジエン化合物の製造方法。The manufacturing method of the phosphorus-containing butadiene compound represented by these.
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US20220227795A1 (en) * | 2019-11-27 | 2022-07-21 | Maruzen Petrochemical Co., Ltd. | Method for manufacturing alkenyl phosphorus compound |
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