JPH0688917B2 - Hydrocarbon conversion method using ethylene - Google Patents
Hydrocarbon conversion method using ethyleneInfo
- Publication number
- JPH0688917B2 JPH0688917B2 JP2214040A JP21404090A JPH0688917B2 JP H0688917 B2 JPH0688917 B2 JP H0688917B2 JP 2214040 A JP2214040 A JP 2214040A JP 21404090 A JP21404090 A JP 21404090A JP H0688917 B2 JPH0688917 B2 JP H0688917B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- mmol
- ligand
- reaction
- compound
- 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.)
- Expired - Lifetime
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 17
- 239000005977 Ethylene Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 13
- 229930195733 hydrocarbon Natural products 0.000 title claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 title description 11
- -1 phosphorus compound Chemical group 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 150000003003 phosphines Chemical class 0.000 claims description 4
- 125000005538 phosphinite group Chemical group 0.000 claims description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 4
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002994 raw material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 4
- 239000004914 cyclooctane Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000010813 internal standard method Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 3
- 239000004913 cyclooctene 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
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- FBGUQAGGWLRXTP-UHFFFAOYSA-N ethylcyclooctane Chemical compound CCC1CCCCCCC1 FBGUQAGGWLRXTP-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 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
- 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
- GUFMBISUSZUUCB-UHFFFAOYSA-N 1,3,5-tritert-butylbenzene Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 GUFMBISUSZUUCB-UHFFFAOYSA-N 0.000 description 1
- KUCAPSLVHGFOHX-UHFFFAOYSA-N 1-methylphosphole Chemical compound CP1C=CC=C1 KUCAPSLVHGFOHX-UHFFFAOYSA-N 0.000 description 1
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical group CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- PBFCLJWSJLLOSW-UHFFFAOYSA-N iridium;tri(propan-2-yl)phosphane Chemical compound [Ir].CC(C)P(C(C)C)C(C)C PBFCLJWSJLLOSW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、置換または未置換の炭化水素類を原料化合物
として用い、これをエチレンで処理することによって、
原料化合物の脱水素体や、原料化合物のエチレン付加体
等を合成する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention uses substituted or unsubstituted hydrocarbons as a raw material compound and treats it with ethylene to give
The present invention relates to a method for synthesizing a dehydrogenated product of a raw material compound, an ethylene adduct of the raw material compound, and the like.
炭素−水素結合を持つ有機化合物の炭素−水素結合を解
裂させ、エチレンと反応させることにより、一般式（Ｉ
〜III）に示すような変換反応を行うことが原理的には
可能である。By cleaving the carbon-hydrogen bond of the organic compound having a carbon-hydrogen bond and reacting with ethylene, the compound of the general formula (I
~ In principle, it is possible to carry out the conversion reaction as shown in III).
R1R2CHCHR3R4＋CH2＝CH2→R1R2C＝CR3R4＋CH3CH3（Ｉ） RH＋CH2＝CH2→RCH2CH3（or RCH＝CH2＋H2） （II） 2RH＋CH2＝CH2→Ｒ−Ｒ＋CH3CH3 （III） しかし、炭化水素類の炭素−水素結合は非常に安定であ
り、これをエチレンと反応させるに充分なまでに活性化
させることは困難である。従来、ロジウムやパラジウム
等の遷移金属錯体存在下、炭化水素とエチレンを反応さ
せる炭化水素の変換法が提案されているが、反応に関与
し得るのは芳香環上の炭素−水素結合に限定されていた
（日本化学会編、「有機金属の化学」、P.184−185、大
日本図書、1989年）。また学術的には、イリジウム等の
遷移金属錯体存在下、パラフィンをt-ブチルエチレンで
処理することによる脱水素法が活発に研究されている
が、オレフィンを１分子合成するために高価なt-ブチル
エチレンを１分子消費する方法は工業的に好ましいとは
言えない（Chemical Review誌、85巻、245頁、1985
年）。同様の脱水素反応をエチレンを用いて行う方法も
提案されているが、230℃付近の高温においてさえ触媒
活性が低く、満足すべき方法とは言えない（特開昭63-2
2034）。R 1 R 2 CHCHR 3 R 4 + CH 2 = CH 2 → R 1 R 2 C = CR 3 R 4 + CH 3 CH 3 (I) RH + CH 2 = CH 2 → RCH 2 CH 3 (or RCH = CH 2 + H 2 ) (II) 2RH + CH 2 = CH 2 → RR + CH 3 CH 3 (III) However, the carbon-hydrogen bond of hydrocarbons is very stable, and it must be activated enough to react with ethylene. It is difficult. Conventionally, a method for converting a hydrocarbon by reacting a hydrocarbon with ethylene in the presence of a transition metal complex such as rhodium or palladium has been proposed, but it is limited to the carbon-hydrogen bond on the aromatic ring that can participate in the reaction. (The Chemical Society of Japan, “Chemistry of Organic Metals”, P.184-185, Dainippon Books, 1989). In addition, academically, the dehydrogenation method by treating paraffin with t-butylethylene in the presence of a transition metal complex such as iridium has been actively studied, but it is expensive to synthesize one molecule of olefin. The method of consuming one molecule of butyl ethylene is not industrially preferable (Chemical Review, Vol. 85, p. 245, 1985).
Year). A method of carrying out the same dehydrogenation reaction using ethylene has also been proposed, but it cannot be said to be a satisfactory method because the catalytic activity is low even at a high temperature of around 230 ° C (JP-A-63-2).
2034).
このような状況に鑑み、本発明者らは炭化水素のエチレ
ン処理による変換法に関して、高い触媒活性を有する錯
体触媒系を見出すことで、前記した問題を解決すべく鋭
意努力検討を行った。In view of such a situation, the present inventors have diligently studied to solve the above-mentioned problems by finding a complex catalyst system having a high catalytic activity with respect to a conversion method of a hydrocarbon by treating with ethylene.
本発明によれば、配位子として少なくとも１個のリン化
合物を含むロジウム錯体の存在下、置換又は未置換の炭
化水素類をエチレンと反応させることを特徴とする炭化
水素類の変換方法が提供される。According to the present invention, there is provided a method for converting hydrocarbons, which comprises reacting a substituted or unsubstituted hydrocarbon with ethylene in the presence of a rhodium complex containing at least one phosphorus compound as a ligand. To be done.
本発明の方法においては、炭化水素類はリン化合物配位
子を含むロジウム錯体によって活性化され、エチレンで
処理することによって、脱水素化合物やエチレン付加物
に変換される。In the method of the present invention, hydrocarbons are activated by a rhodium complex containing a phosphorus compound ligand and converted to a dehydrogenated compound or an ethylene adduct by treating with ethylene.
触媒 本発明で用いるロジウム錯体触媒においては、その配位
子の内の少なくとも一つが、一般式R1R2R3P,（R10）R2R
3P,（R10）（R20）R3P,または（R10）（R20）（R30）Ｐ
（式中、R1、R2、R3は炭素数１から20のアルキル基、ア
リール基、アラルキル基またはシクロアルキル基を示
し、R1、R2、R3は互いに同じであっても異なっていても
良い）で表されるホスフィン類、ホスフィナイト類、ホ
スホナイト類、またはホスファイト類であることが必要
である。Catalyst In the rhodium complex catalyst used in the present invention, at least one of the ligands has the general formula R 1 R 2 R 3 P, (R 1 0) R 2 R
3 P, (R 1 0) (R 2 0) R 3 P, or (R 1 0) (R 2 0) (R 3 0) P
(In the formula, R 1 , R 2 and R 3 represent an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group or a cycloalkyl group, and R 1 , R 2 and R 3 are the same or different. Phosphines, phosphinites, phosphonites, or phosphites represented by
好適な配位子としてさらに具体的には、トリメチルホス
フィン、トリエチルホスフィ、トリブチルホスフィン、
トリオクチルホスフィン、トリシクロヘキシルホスフィ
ン、トリベンジルホスフィン、トリフェニルホスフィ
ン、Ｐ−メチルホスホレン、Ｐ−メチルホスホール、等
のホスフィン、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、
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、トリメチルホスファイ
ト、トリエチルホスファイト、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る。More specifically, suitable ligands include trimethylphosphine, triethylphosphine, tributylphosphine,
Phosphines such as trioctylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenylphosphine, P-methylphosphorene, P-methylphosphole, and the like, phosphinites such as methyldimethylphosphinite, methyldiphenylphosphinite, and the like,
Examples thereof include phosphonites such as dimethyl methylphosphonite and dimethylphenylphosphonite, and phosphites such as trimethylphosphite, triethylphosphite and trimethylolpropane phosphite.
本発明で用いられる触媒は１価のロジウムホスフィン錯
体が好適であるが、さらに具体的にはRhCl（CH2＝CH2）
L2,〔RhClL2〕2,またはRhClL3等を例示することができ
る（Ｌは前記一般式で表わされる含リン配位子）。ま
た、前駆体として〔RhCl（CH2＝CH2）２〕2,〔RhCl（cy
clo-C8H14）２〕２等のロジウム化合物を用いて系中（i
n situ）で活性な触媒を発生させて用いてもよい。The catalyst used in the present invention is preferably a monovalent rhodium phosphine complex, and more specifically, RhCl (CH 2 = CH 2 )
L 2 , [RhClL 2 ] 2 or RhClL 3 can be exemplified (L is a phosphorus-containing ligand represented by the above general formula). In addition, as a precursor, [RhCl (CH 2 = CH 2 ) 2 ] 2 , [RhCl (cy
clo-C 8 H 14 ) 2 ] 2 and other rhodium compounds are used in the system (i
You may generate and use an active catalyst in (n situ).
原料化合物 本発明で用いられる原料化合物は、炭素−水素結合（シ
グマ結合）を少なくとも１個有する化合物であり、脂肪
族、芳香族、複素環化合物を問わず使用できる。また、
このような化合物は、各種置換基を含むことができる。
このような置換基の具体例としては、例えば、アルコキ
シ基、アリーロキシ基、アシル基、アシロキシ基、アル
コキシカルボニル基、シアノ基、ハロゲン原子等が挙げ
られる。原料化合物を具体的に例示すると、メタン、エ
タン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタ
ン、オクタン、ノナン、デカン、シクロプロパン、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、ベンゼン、トルエン、エチルベン
ゼン、テトラヒドロフラン、ジエチルエーテル、フェニ
ルエチルエーテル、酢酸エチル等が挙げられる。Raw Material Compound The raw material compound used in the present invention is a compound having at least one carbon-hydrogen bond (sigma bond), and may be an aliphatic, aromatic or heterocyclic compound. Also,
Such compounds may contain various substituents.
Specific examples of such a substituent include an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a halogen atom and the like. Specific examples of the raw material compounds are methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, cyclopropane, cyclopentane, cyclohexane, cyclooctane, cyclododecane, decalin, benzene, toluene, ethylbenzene. , Tetrahydrofuran, diethyl ether, phenylethyl ether, ethyl acetate and the like.
反応条件 上記のような反応は以下のような反応条件下に行うこと
が望ましい。Reaction Conditions It is desirable to carry out the above reaction under the following reaction conditions.
反応温度は‐50〜350℃、通常は20〜250℃である。ま
た、エチレンの圧力は反応温度において0.1〜500気圧、
好ましくは１〜100気圧の範囲である。The reaction temperature is -50 to 350 ° C, usually 20 to 250 ° C. The pressure of ethylene is 0.1 to 500 atm at the reaction temperature,
It is preferably in the range of 1 to 100 atm.
反応に際しては、溶媒は必ずしも必要ではないが、2,2,
5,5-テトラメチルヘキサン、1,3,5-トリ‐t-ブチルベン
ゼン等の不活性な溶媒を用いて反応を行うことも本発明
の有利な態様に含まれる。A solvent is not always necessary for the reaction, but 2,2,
It is also included in an advantageous aspect of the present invention to carry out the reaction using an inert solvent such as 5,5-tetramethylhexane or 1,3,5-tri-t-butylbenzene.
触媒としての前記ロジウム錯体は、原料化合物１モルに
対して好ましくは0.0001〜0.5モル、さらに好ましくは
0.001〜0.05モル程度の量用いられる。The rhodium complex as a catalyst is preferably 0.0001 to 0.5 mol, and more preferably 1 mol of the raw material compound.
It is used in an amount of about 0.001 to 0.05 mol.
生成物の分離は、反応液を蒸留、クロマトグラフィー、
再結晶等の通常の精製操作に付することにより容易に実
施される。The products can be separated by distilling the reaction solution, chromatography,
It can be easily carried out by subjecting it to ordinary purification operations such as recrystallization.
本発明によれば、比較的低温で、炭化水素類を種々の有
用化合物に変換することができ、その産業的意義は多大
である。According to the present invention, hydrocarbons can be converted into various useful compounds at a relatively low temperature, and its industrial significance is great.
次に本発明を実施例によってさらに具体的に説明する。 Next, the present invention will be described more specifically by way of examples.
実施例１ μ‐ジクロロテトラキス（トリメチルホスフィン）二ロ
ジウム（2.9mg,0.005mmol）及びシクロオクタン（5ml）
を窒素雰囲気下、オートクレーブにしこみ、エチレンを
室温で30atmまで圧入後、170℃で15時間加熱した。冷却
後、液相をガスクロマトグラフィー（内部標準法）で分
析したところ、シクロオクテン（0.092mmol）及びエチ
ルシクロオクタン（0.0021mmol）が生成していることが
分かった。Example 1 μ-Dichlorotetrakis (trimethylphosphine) dirhodium (2.9 mg, 0.005 mmol) and cyclooctane (5 ml)
Was squeezed into an autoclave under a nitrogen atmosphere, ethylene was press-fitted to 30 atm at room temperature, and then heated at 170 ° C. for 15 hours. After cooling, the liquid phase was analyzed by gas chromatography (internal standard method), and it was found that cyclooctene (0.092 mmol) and ethylcyclooctane (0.0021 mmol) were produced.
実施例２ μ‐ジクロロテトラキス（トリメチルホスフィン）二ロ
ジウム（2.9mg,0.005mmol）及びシクロオクタン（5ml）
を窒素雰囲気下、オートクレーブにしこみ、エチレンを
室温で30atmまで圧入後、230℃で15時間加熱した。冷却
後、液相をガスクロマトグラフィー（内部標準法）で分
析したところ、シクロオクテン（0.11mmol）及びエチル
シクロオクタン（0.25mmol）が生成していることが分か
った。Example 2 μ-Dichlorotetrakis (trimethylphosphine) dirhodium (2.9 mg, 0.005 mmol) and cyclooctane (5 ml)
Was squeezed into an autoclave under a nitrogen atmosphere, ethylene was press-fitted to 30 atm at room temperature, and then heated at 230 ° C. for 15 hours. After cooling, the liquid phase was analyzed by gas chromatography (internal standard method), and it was found that cyclooctene (0.11 mmol) and ethylcyclooctane (0.25 mmol) were produced.
実施例３ μ‐ジクロロテトラキス（トリメチルホスフィン）二ロ
ジウム（2.9mg,0.005mmol）及びベンゼン（5ml）を窒素
雰囲気下、オートクレーブにしこみ、エチレンを室温で
30atmまで圧入後、170℃で15時間加熱した。冷却後、液
相をガスクロマトグラフィー（内部標準法）で分析した
ところ、スチレン及びエチルベンゼンが検出された。Example 3 μ-Dichlorotetrakis (trimethylphosphine) dirhodium (2.9 mg, 0.005 mmol) and benzene (5 ml) were put into an autoclave under a nitrogen atmosphere, and ethylene was added at room temperature.
After pressurizing to 30 atm, it was heated at 170 ° C. for 15 hours. After cooling, the liquid phase was analyzed by gas chromatography (internal standard method), and styrene and ethylbenzene were detected.
比較例１ ペンタヒドロビス（トリイソプロピルホスフィン）イリ
ジウム（5.2mg,0.010mmol）及びシクロオクタン（5ml）
を窒素雰囲気下、オートクレーブにしこみ、エチレンを
室温で30atmまで圧入後、170℃で15時間加熱した。冷却
後、液相をガスクロマトグラフィー（内部標準法）で分
析したところ、シクロオクテンの生成量は、0.0028mmol
にすぎなかった。Comparative Example 1 Pentahydrobis (triisopropylphosphine) iridium (5.2 mg, 0.010 mmol) and cyclooctane (5 ml)
Was squeezed into an autoclave under a nitrogen atmosphere, ethylene was press-fitted to 30 atm at room temperature, and then heated at 170 ° C. for 15 hours. After cooling, the liquid phase was analyzed by gas chromatography (internal standard method). As a result, the amount of cyclooctene produced was 0.0028 mmol.
It was nothing more than
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Claims (3)
を含むロジウム錯体の存在下、置換または未置換の炭化
水素類をエチレンと反応させることを特徴とする炭化水
素類の変換方法。1. A method for converting hydrocarbons, which comprises reacting a substituted or unsubstituted hydrocarbon with ethylene in the presence of a rhodium complex containing at least one phosphorus compound as a ligand.
ト類、ホスホナイト類及びホスファイト類の中から選ば
れた少なくとも１種である請求項１記載の方法。2. The method according to claim 1, wherein the phosphorus compound is at least one selected from phosphines, phosphinites, phosphonites and phosphites.
を含むロジウム錯体が、一般式 RhCl（CH2＝CH2）L2 〔RhClL2〕２ 又は RhClL3 （式中のＬはホスフィン類、ホスフィナイト類、ホスホ
ナイト類及びホスファイト類の中から選ばれた配位子で
ある） で表わされる錯体である請求項１又は２記載の方法。3. A rhodium complex containing at least one phosphorus compound as a ligand of the general formula RhCl (CH 2 = CH 2) L 2 [RhClL 2] 2 or RhClL 3 (L in the formula phosphines, The method according to claim 1 or 2, wherein the complex is a ligand selected from phosphinites, phosphonites and phosphites.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2214040A JPH0688917B2 (en) | 1990-08-13 | 1990-08-13 | Hydrocarbon conversion method using ethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2214040A JPH0688917B2 (en) | 1990-08-13 | 1990-08-13 | Hydrocarbon conversion method using ethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0499733A JPH0499733A (en) | 1992-03-31 |
| JPH0688917B2 true JPH0688917B2 (en) | 1994-11-09 |
Family
ID=16649284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2214040A Expired - Lifetime JPH0688917B2 (en) | 1990-08-13 | 1990-08-13 | Hydrocarbon conversion method using ethylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0688917B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6298438B2 (en) * | 2014-11-28 | 2018-03-20 | 旭化成株式会社 | Process for producing hydrocarbons |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670621A (en) * | 1986-05-05 | 1987-06-02 | Ethyl Corporation | Catalytic synthesis of olefins from paraffins |
-
1990
- 1990-08-13 JP JP2214040A patent/JPH0688917B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0499733A (en) | 1992-03-31 |
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