JPH01121225A - Dehydrogenation of hydrocarbons - Google Patents
Dehydrogenation of hydrocarbonsInfo
- Publication number
- JPH01121225A JPH01121225A JP27798687A JP27798687A JPH01121225A JP H01121225 A JPH01121225 A JP H01121225A JP 27798687 A JP27798687 A JP 27798687A JP 27798687 A JP27798687 A JP 27798687A JP H01121225 A JPH01121225 A JP H01121225A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- rhodium
- hydrocarbons
- ethylenically unsaturated
- organophosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 19
- 238000006356 dehydrogenation reaction Methods 0.000 title abstract 2
- 239000010948 rhodium Substances 0.000 claims abstract description 24
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 13
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005538 phosphinite group Chemical group 0.000 claims abstract description 5
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 abstract description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- -1 ethylene, propylene, hexene Chemical class 0.000 abstract description 3
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 abstract description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003003 phosphines Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-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
- QRRVMWPNMMLSGD-UHFFFAOYSA-N (2-dimethylphosphanylphenyl)-dimethylphosphane Chemical compound CP(C)C1=CC=CC=C1P(C)C QRRVMWPNMMLSGD-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- ZKWQSBFSGZJNFP-UHFFFAOYSA-N 1,2-bis(dimethylphosphino)ethane Chemical compound CP(C)CCP(C)C ZKWQSBFSGZJNFP-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
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- RFFCUDDJJDOFLS-UHFFFAOYSA-N 1-cyclohexylcyclohexene Chemical compound C1CCCCC1C1=CCCCC1 RFFCUDDJJDOFLS-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- GZDVNUHKYJNVNT-UHFFFAOYSA-N 3-dimethylphosphanylpropyl(dimethyl)phosphane Chemical compound CP(C)CCCP(C)C GZDVNUHKYJNVNT-UHFFFAOYSA-N 0.000 description 1
- FNAYAXPWEKXHQU-UHFFFAOYSA-N 4-dimethylphosphanylbutyl(dimethyl)phosphane Chemical compound CP(C)CCCCP(C)C FNAYAXPWEKXHQU-UHFFFAOYSA-N 0.000 description 1
- WFLOFEOFRYPJED-UHFFFAOYSA-N CC(=O)CC([CH2-])=O Chemical group CC(=O)CC([CH2-])=O WFLOFEOFRYPJED-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- ZPWOOKQUDFIEIX-UHFFFAOYSA-N cyclooctyne Chemical compound C1CCCC#CCC1 ZPWOOKQUDFIEIX-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZXMSTCRBSAVFDO-UHFFFAOYSA-N dimethoxy(methyl)phosphane Chemical compound COP(C)OC ZXMSTCRBSAVFDO-UHFFFAOYSA-N 0.000 description 1
- LMZLQYYLELWCCW-UHFFFAOYSA-N dimethoxy(phenyl)phosphane Chemical compound COP(OC)C1=CC=CC=C1 LMZLQYYLELWCCW-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ODXKYOFRPVSRTK-UHFFFAOYSA-N methoxy(dimethyl)phosphane Chemical compound COP(C)C ODXKYOFRPVSRTK-UHFFFAOYSA-N 0.000 description 1
- OAADXJFIBNEPLY-UHFFFAOYSA-N methoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(OC)C1=CC=CC=C1 OAADXJFIBNEPLY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- RAVACSWYIIPFFV-UHFFFAOYSA-N tris[(4-methoxyphenyl)methyl]phosphane Chemical compound C1=CC(OC)=CC=C1CP(CC=1C=CC(OC)=CC=1)CC1=CC=C(OC)C=C1 RAVACSWYIIPFFV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、エチレン性不飽和結合の生成法に関し、より
詳しくは、炭化水素を脱水素させてエチレン性不飽和結
合を生成させることからなるエチレン性不飽和化合物の
製造技術に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing ethylenically unsaturated bonds, and more specifically, it involves dehydrogenating hydrocarbons to produce ethylenically unsaturated bonds. This invention relates to a technology for producing ethylenically unsaturated compounds.
（従来の技術）
現下の石油化学原料体系に於ては、基礎原料であるエチ
レン性不飽和化合物の製造は大部分炭化水素類の熱分解
反応によっている。(Prior Art) In the current petrochemical raw material system, the production of ethylenically unsaturated compounds, which are basic raw materials, is mostly carried out by thermal decomposition reactions of hydrocarbons.
（発明が解決しようとする問題点）
しかし、この熱分解には７００〜９００℃もの高温を要
するのが普通であり、しかも炭素数の異なる複雑な混合
物しか得られず、所望の炭素数のエチレン性不飽和化合
物収率は一般的に低い。(Problems to be solved by the invention) However, this thermal decomposition usually requires a high temperature of 700 to 900°C, and only a complex mixture with different carbon numbers can be obtained. The yield of sexually unsaturated compounds is generally low.
このように従来のオレフィン製造法は必ずしもこのよう
な状況に鑑み、本発明者らは、炭化水素類を原料として
エチレン性不飽和化合物を効率的に製造しうる新規方法
について、鋭意検索・研究を行った。In view of this situation, the present inventors have been conducting intensive search and research into new methods that can efficiently produce ethylenically unsaturated compounds using hydrocarbons as raw materials. went.
（目的を解決するための手段）
本発明は、ホスフィン、ホスホナイト、ホスフィナイト
およびホスファイトから成る群から選ばれる少なくとも
一種の有機リン化合物のロジウム錯体の存在下、または
少なくとも一種の該有機リン化合物とロジウム化合物と
の共存下に、炭化水素に光照射することを特徴とする炭
化水素類の脱水素法を要旨とするものであり、これによ
り、エチレン性不飽和化合物の効率的な製造法が提供さ
れる。(Means for Solving the Object) The present invention provides a method for combining rhodium with at least one organic phosphorus compound in the presence of a rhodium complex of at least one organic phosphorus compound selected from the group consisting of phosphine, phosphonite, phosphinite, and phosphite. The gist of this is a method for dehydrogenating hydrocarbons, which is characterized by irradiating the hydrocarbons with light in the coexistence of a chemical compound, thereby providing an efficient method for producing ethylenically unsaturated compounds. Ru.
本発明の炭化水素類の脱水素法は、ホスフィン、ホスホ
ナイト、ホスフィナイトおよびホスファイトからなる群
から選ばれた少なくとも一種の有機リン化合物のロジウ
ム錯体の存在下に行われる。The method for dehydrogenating hydrocarbons of the present invention is carried out in the presence of a rhodium complex of at least one organic phosphorus compound selected from the group consisting of phosphine, phosphonite, phosphinite, and phosphite.
これらの有機リン化合物におけるリンは、すべて３価で
あり、具体的には、単座配位性の有機リン化合物（ＰＲ
’、で示す）として例えばトリメチルホスフィン、トリ
エチルホスフィン、トリブチルホスフィン、トリオクチ
ルホスフィン、トリフェニルホスフィン、トリ（ｐ−ト
リル）ホスフィン。Phosphorus in these organophosphorus compounds is all trivalent, and specifically, monodentate organophosphorus compounds (PR
', for example, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tri(p-tolyl)phosphine.
トリ（ｐ−アニシル）ホスフィン等の鎖状ホスフィン、
ｐ−メチルホスホール、ｐ−メチルホスホール等の環状
ホスフィン、ジメチル メチルホスホナイト、ジメチル
フェニルホスホナイト等のホスホナイト、メチル ジ
メチルホスフィナイト、メチル ジフェニルホスフィナ
イト等のホスフィナイト、およびトリエチルホスファイ
ト、トリフェニルホスファイト、トリメチロールプロパ
ンホスファイト等のホスファイトを挙げることができ、
また２座配位性の有機リン化合物（Ｒ２□Ｐ−ＰＲ２□
で示す）として、例えば１，２−ビス（ジメチルホスフ
ィノ）エタン、１，３−ビス（ジメチルホスフィノ）プ
ロパン、１，４−ビス（ジメチルホスフィノ）ブタン、
１，２−ビス（ジフェニルホスフィノ）エタン、１，４
−ビス（ジフェニル（ジメチルホスフィノ）−０−キシ
レン、１，２−ビス（ジメチルホスフィノ）ベンゼン等
のビスホスフィンが挙げられる。Chain phosphine such as tri(p-anisyl)phosphine,
Cyclic phosphines such as p-methylphosphole and p-methylphosphole; phosphonites such as dimethyl methylphosphonite and dimethyl phenylphosphonite; phosphinites such as methyl dimethylphosphinite and methyl diphenylphosphinite; and triethyl phosphite and triethyl phosphite. Phosphites such as phenyl phosphite and trimethylolpropane phosphite can be mentioned,
In addition, bidentate organophosphorus compounds (R2□P-PR2□
), for example, 1,2-bis(dimethylphosphino)ethane, 1,3-bis(dimethylphosphino)propane, 1,4-bis(dimethylphosphino)butane,
1,2-bis(diphenylphosphino)ethane, 1,4
Bisphosphines such as -bis(diphenyl(dimethylphosphino)-0-xylene and 1,2-bis(dimethylphosphino)benzene) can be mentioned.
これら有機リン化合物のロジウム錯体としては、種々の
構造のものを用いることができるが、−価のロジウム錯
体が好ましい。As the rhodium complexes of these organic phosphorus compounds, those having various structures can be used, but -valent rhodium complexes are preferred.
具体的には例えばＲｈＸ （ＰＲ’ｉ）ａ （ＰＲ’ａ
は前記内容を示す。また又は水素、ハロゲン原子、水酸
基、シアノ基、アルコキシ基、カルボキシラド基および
チオシアナト基からなる群から選ばれる基を示す。以下
同様） 、Ｒｈ Ｘ （Ｃｏ） （ＰＲ’ ３）２、Ｒ
ｈ Ｘ （ｃｏ）、 （ｐＲ１３）、Ｒｈ Ｘ （Ｃｏ
）ｚ （ＰＲ’□）２、Ｒｈ Ｘ （ＰＲ’ 、 ”）
い［Ｒｈ（ＰＲ’３）４）Ｙ（ＹはＰＦＧ、 Ｂ（ＣＧ
Ｈ，、）４、ＢＦ４． ＣｌＯ４および前記Ｘからなる
群から選ばれる基を示す。以下同様）、 （Ｒｈ（ｐ
Ｒ２３）、（ｃＮＲ”）２）Ｙ（ＧＮＰはイソニトリル
を、Ｒ２はアルキルまたはアリール基を示す。以下同様
）、（Ｒｈ（ＰＲ’、）、（ＣＮＲ”）３）Ｙ、 Ｒｈ
Ｘ（Ｃｏ）（Ｒ２□Ｐ−ＰＲ”□）などを挙げることが
できる。Specifically, for example, RhX (PR'i)a (PR'a
indicates the above content. It also represents a group selected from the group consisting of hydrogen, a halogen atom, a hydroxyl group, a cyano group, an alkoxy group, a carboxylad group, and a thiocyanato group. The same applies hereafter), Rh X (Co) (PR' 3)2, R
h X (co), (pR13), Rh X (Co
)z (PR'□)2, Rh X (PR', ”)
[Rh(PR'3)4)Y(Y is PFG, B(CG
H,, )4, BF4. It represents a group selected from the group consisting of ClO4 and the above X. (Similarly below), (Rh(p
R23), (cNR'')2)Y (GNP represents isonitrile, R2 represents an alkyl or aryl group. The same applies hereinafter), (Rh(PR',), (CNR'')3)Y, Rh
Examples include X(Co)(R2□P-PR''□).
せ、系中においてロジウム錯体を形成させる方法によっ
ても、好まし〈実施することができる。It can also be preferably carried out by a method of forming a rhodium complex in the system.
このような目的のために好ましく用いられるロジウム化
合物としては、Ｒｈ （ａｃａｃ） （Ｃｏ）、 （ａ
ｃａｅはアセチルアセトナイド基を示す）、（ＲｈＸ（
Ｃｏ）、）２、（Ｒｈ Ｘ （ＤＨ） ） 、 （ＤＥ
はノルボルナジェン、１．５−シクロオクタジエン、ま
たは１，５−へキサジエンを示す） −［ＲｈＸ （Ｕ
Ｎ）ｚ）ｚ （ＥＮはエチレンまたはシクロオクチンを
示す）、 ＲｈＸ（Ｃｏ）（ＰＲ’、）、などが挙げら
れる。Rhodium compounds preferably used for this purpose include Rh (acac) (Co), (a
cae represents an acetylacetonide group), (RhX(
Co), )2, (Rh X (DH) ), (DE
represents norbornadiene, 1,5-cyclooctadiene, or 1,5-hexadiene) -[RhX (U
N)z)z (EN represents ethylene or cyclooctyne), RhX(Co)(PR', ), and the like.
本発明の方法に用いられる炭化水素は少なくとも１つの
水素原子を結合した炭素原子が隣接して単結合で結合し
た部分構造を有するものである。The hydrocarbon used in the method of the present invention has a partial structure in which carbon atoms bonded to at least one hydrogen atom are bonded adjacently through single bonds.
その具体例としては、エタン、プロパン、ブタン、ペン
タン、ヘキサン、オクタン、イソペンタン、イソオクタ
ン、デカン、エイコサン、エチルベンゼン、ｎ−ヘキシ
ルベンゼン、イソプロピルベンゼン、ドデシルベンゼン
、α−又はβ−エチルナフタレン、シクロペンタン、シ
クロヘキサン、シクロオクタン、シクロドデカン、デカ
リン、テトラリン等を挙げることができるが、前記の部
分構造を有する炭化水素誘導体であれば、これらに限定
されることなく好適に用いることが出来、置換基を有す
る化合物を用いることも可能である。Specific examples include ethane, propane, butane, pentane, hexane, octane, isopentane, isooctane, decane, eicosane, ethylbenzene, n-hexylbenzene, isopropylbenzene, dodecylbenzene, α- or β-ethylnaphthalene, cyclopentane, Examples include cyclohexane, cyclooctane, cyclododecane, decalin, tetralin, etc., but any hydrocarbon derivative having the above-mentioned partial structure can be suitably used without being limited to these. It is also possible to use compounds.
これら炭化水素類のロジウム錯体またはロジウム化合物
に対する使用量は、任意に選ぶことができ、これら炭化
水素類が液体である場合には、この炭化水素類自体を溶
媒量用いることも有利な方法である。The amount of these hydrocarbons to be used relative to the rhodium complex or rhodium compound can be selected arbitrarily, and when these hydrocarbons are liquid, it is also advantageous to use the amount of the hydrocarbons themselves as a solvent. .
本発明における反応は、光照射下に進行するが、光の波
長領域はいわゆる紫外・可視光領域であれば良く、水銀
燈、タングステンランプ、ハロゲンランプ、キセノンラ
ンプ、太陽光などの照射が好（発明の効果）
本発明の炭化水素類の脱水素法によれば、入手容易な炭
化水素を温和な条件下にエチレン、プロピレン、ヘキセ
ン、シクロペンテン、シクロヘキセン、シクロドデセン
、スチレン等のエチレン性不飽和結合を有する化合物に
変換することが出来る。The reaction in the present invention proceeds under light irradiation, but the wavelength range of the light may be in the so-called ultraviolet/visible light range, and irradiation with a mercury lamp, tungsten lamp, halogen lamp, xenon lamp, sunlight, etc. is preferable (invention According to the method for dehydrogenating hydrocarbons of the present invention, easily available hydrocarbons having ethylenically unsaturated bonds such as ethylene, propylene, hexene, cyclopentene, cyclohexene, cyclododecene, styrene, etc. can be extracted under mild conditions. It can be converted into a compound.
（実施例） 次に実施例により、本発明をさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
生成物はＧＣ−ＭＳによっても構造を確認した。The structure of the product was also confirmed by GC-MS.
実施例１゜
内容積７０ｍ１のＰｙｒｅｘ製、内部照射型光反応容器
にクロロカルボニルビス（トリメチルホスフィン）ロジ
ウム６．７ｍｇ（０，０２１ｍｍｏｌ）のシクロヘキサ
ン溶液（３０ｍｌ）をしこみ、凍結脱気を２回行った後
、−気圧の窒素を導入し、容器を密閉した。Example 1 A cyclohexane solution (30 ml) containing 6.7 mg (0,021 mmol) of chlorocarbonylbis(trimethylphosphine)rhodium was poured into a Pyrex internal irradiation type photoreaction vessel with an internal volume of 70 ml, and freeze-degassed twice. After that, -atmospheric nitrogen was introduced and the container was sealed.
１００Ｗの高圧水銀灯を用いて光照射しながら１６．５
時間攪拌した後、反応液をガスクロマトグラフィーで分
析したところ、１３７７２％／Ｒｈ（Ｒｈ錯体に対する
モル百分率）のシクロヘキセン、２７４％／Ｒｈのベン
ゼン、及び約４００％／Ｒｈの二量体生成物（ビシクロ
ヘキセン、ビシクロヘキサン及びシクロへキシルシクロ
ヘキセンの混合物）が検出された。また気相には、シク
ロヘキセンの生成に対応する量の水素が検出された。16.5 while irradiating light using a 100W high-pressure mercury lamp.
After stirring for an hour, the reaction solution was analyzed by gas chromatography and found to contain 13772%/Rh (mole percentage relative to the Rh complex) of cyclohexene, 274%/Rh of benzene, and about 400%/Rh of the dimer product ( Bicyclohexene, a mixture of bicyclohexane and cyclohexylcyclohexene) were detected. Additionally, an amount of hydrogen corresponding to the production of cyclohexene was detected in the gas phase.
実施例２゜
溶媒としてネオヘキサンを用いる以外は、実施例１．と
同様にして反応を行い、２３２％／Ｒｈの＝７−
ネオヘキセンを得た。Example 2° Example 1 except that neohexane was used as the solvent. The reaction was carried out in the same manner as above to obtain 7-neohexene of 232%/Rh.
実施例３゜
内容積７０ｍ１のＰｙｒｅｘ製、内部照射型光反応容器
にクロロカルボニルビス（トリメチルホスフィン）ロジ
ウム６．７ｍｇ（０，０２１ｍｍｏｌ）のシクロオクタ
ン溶液（ａｏｍｌ）をしこみ、凍結脱気を二回行った後
、−気圧の窒素を導入した。気相部に約８ｍｌ／ｍｉｎ
の流速で窒素を流しながら、液相部を１００Ｗの高圧水
銀灯照射下に１６．５時間攪拌した。Example 3 A cyclooctane solution (aoml) containing 6.7 mg (0,021 mmol) of chlorocarbonylbis(trimethylphosphine)rhodium was poured into a Pyrex internal irradiation type photoreaction vessel with an internal volume of 70 ml, and freeze-degassed twice. After this, -atmospheres of nitrogen were introduced. Approximately 8ml/min in the gas phase
The liquid phase was stirred for 16.5 hours under irradiation with a 100 W high-pressure mercury lamp while flowing nitrogen at a flow rate of .
ロオクテンの混合物）が検出された。A mixture of looctenes) was detected.
注）１．９８ｍ１に相当。Note) Equivalent to 1.98m1.
Claims (1)
びホスファイトから成る群から選ばれる少なくとも一種
の有機リン化合物のロジウム錯体の存在下、または少な
くとも一種の該有機リン化合物とロジウム化合物との共
存下に、置換又は未置換の炭化水素に光照射することを
特徴とする炭化水素類の脱水素法。(1) In the presence of a rhodium complex of at least one organic phosphorus compound selected from the group consisting of phosphine, phosphonite, phosphinite, and phosphite, or in the coexistence of at least one organic phosphorus compound and a rhodium compound, substituted or unsubstituted A method for dehydrogenating hydrocarbons, which is characterized by irradiating substituted hydrocarbons with light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27798687A JPH01121225A (en) | 1987-11-02 | 1987-11-02 | Dehydrogenation of hydrocarbons |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27798687A JPH01121225A (en) | 1987-11-02 | 1987-11-02 | Dehydrogenation of hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01121225A true JPH01121225A (en) | 1989-05-12 |
| JPH0251887B2 JPH0251887B2 (en) | 1990-11-08 |
Family
ID=17591034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27798687A Granted JPH01121225A (en) | 1987-11-02 | 1987-11-02 | Dehydrogenation of hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01121225A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7626042B2 (en) | 2002-06-06 | 2009-12-01 | Institute Of Medicinal Molecular Design, Inc. | O-substituted hydroxyaryl derivatives |
-
1987
- 1987-11-02 JP JP27798687A patent/JPH01121225A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7626042B2 (en) | 2002-06-06 | 2009-12-01 | Institute Of Medicinal Molecular Design, Inc. | O-substituted hydroxyaryl derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0251887B2 (en) | 1990-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sakakura et al. | Carbonylation of hydrocarbons via carbon-hydrogen activation catalyzed by RhCl (CO)(PMe3) 2 under irradiation | |
| Hayashi et al. | Catalytic asymmetric hydroformylation by the use of rhodium-complexes of chiral bidentate phosphorus ligands bearing saturated ring skeletons. | |
| Touzani et al. | PAMAM dendrimer-palladium complex catalyzed synthesis of five-, six-or seven membered ring lactones and lactams by cyclocarbonylation methodology | |
| Busetto et al. | Bridging vinylalkylidene transition metal complexes | |
| Doherty et al. | Selectivity for the methoxycarbonylation of ethylene versus CO ethylene copolymerization with catalysts based on C4-bridged bidentate phosphines and phospholes | |
| Field et al. | Protonation and rearrangement of bis (acetylide) complexes of iron: formation of coordinated. eta. 3-butenynes | |
| Ungváry | Application of transition metals in hydroformylation. Annual survey covering the year 2000 | |
| Kwong et al. | A general synthesis of aryl phosphines by palladium catalyzed phosphination of aryl bromides using triarylphosphines | |
| Thiel et al. | The broad diversity of CpCo (I) complexes | |
| JPH01121225A (en) | Dehydrogenation of hydrocarbons | |
| JPH0541612B2 (en) | ||
| Sivaramakrishna et al. | Synthesis, structure and reactivity of cis-[PtL2 (1-alkenyl) 2] complexes | |
| JPH0518761B2 (en) | ||
| JPH0196162A (en) | Production of schiff bases | |
| Moulis | Hydroformylation and Aldehyde-Water Shift Catalysis by Dirhodium Tetraphosphine Complexes | |
| Krug | Novel insertion reactions of aldehydes, imines and alkenes of aryl and amido complexes of rhodium (I) and nickel (II) | |
| Franks | The synthesis, characterization, and reactivity of some iridium (III) dicationic complexes | |
| JP2580507B2 (en) | Dehydrogenation of hydrocarbons | |
| Rothstein | Nucleophilic Palladium Carbenes Utilizing Metal-Ligand Cooperativity towards Small Molecule Activations | |
| Gunay | Carbon-carbon bond activation of acetylene derivatives via photolysis of platinum complexes | |
| JPH0688917B2 (en) | Hydrocarbon conversion method using ethylene | |
| Baker | 20 Organometallic chemistry of monometallic species | |
| Franks | The Synthesis and Characterization of Some Ir (III) Dicationic Complexes | |
| Thiel | Synthesis of novel cyclopentadienyl cobalt (I)-complexes and their application in [2+ 2+ 2] cycloaddition reactions | |
| Paige | The synthesis, co-ordination chemistry and catalytic applications of phosphine ligands containing long-chain perfluoro-alkyl groups |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |