JPH02152973A - Production of dibenzofurans - Google Patents
Production of dibenzofuransInfo
- Publication number
- JPH02152973A JPH02152973A JP30599988A JP30599988A JPH02152973A JP H02152973 A JPH02152973 A JP H02152973A JP 30599988 A JP30599988 A JP 30599988A JP 30599988 A JP30599988 A JP 30599988A JP H02152973 A JPH02152973 A JP H02152973A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- raw material
- dibenzofurans
- cyclohexenylcyclohexanone
- cyclohexenylcyclohexanones
- 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
- 150000004826 dibenzofurans Chemical class 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical class O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 9
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 23
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 16
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 235000010292 orthophenyl phenol Nutrition 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- YTWWBKKPWACPPB-UHFFFAOYSA-N 2-cyclohexylcyclohexan-1-ol Chemical compound OC1CCCCC1C1CCCCC1 YTWWBKKPWACPPB-UHFFFAOYSA-N 0.000 description 2
- SOXKACFYZDDBDY-UHFFFAOYSA-N 4-methyl-2-(4-methylcyclohexen-1-yl)cyclohexan-1-one Chemical compound C1C(C)CCC(C2C(CCC(C)C2)=O)=C1 SOXKACFYZDDBDY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004306 orthophenyl phenol Substances 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- PCTMTFRHKVHKIS-BMFZQQSSSA-N (1s,3r,4e,6e,8e,10e,12e,14e,16e,18s,19r,20r,21s,25r,27r,30r,31r,33s,35r,37s,38r)-3-[(2r,3s,4s,5s,6r)-4-amino-3,5-dihydroxy-6-methyloxan-2-yl]oxy-19,25,27,30,31,33,35,37-octahydroxy-18,20,21-trimethyl-23-oxo-22,39-dioxabicyclo[33.3.1]nonatriaconta-4,6,8,10 Chemical compound C1C=C2C[C@@H](OS(O)(=O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2.O[C@H]1[C@@H](N)[C@H](O)[C@@H](C)O[C@H]1O[C@H]1/C=C/C=C/C=C/C=C/C=C/C=C/C=C/[C@H](C)[C@@H](O)[C@@H](C)[C@H](C)OC(=O)C[C@H](O)C[C@H](O)CC[C@@H](O)[C@H](O)C[C@H](O)C[C@](O)(C[C@H](O)[C@H]2C(O)=O)O[C@H]2C1 PCTMTFRHKVHKIS-BMFZQQSSSA-N 0.000 description 1
- ZGYVLTVJKZLTPQ-UHFFFAOYSA-N 2,6-dimethyl-1-benzofuran Chemical compound C1=C(C)C=C2OC(C)=CC2=C1 ZGYVLTVJKZLTPQ-UHFFFAOYSA-N 0.000 description 1
- WEWZILAIHLFVHK-UHFFFAOYSA-N 2-hex-1-enylcyclohexan-1-one Chemical compound CCCCC=CC1CCCCC1=O WEWZILAIHLFVHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical class *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas 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
- 150000002815 nickel Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ジベンゾフラン類の製法に関し、さらに詳し
くは、２−シクロヘキセニルシクロヘキサノン類を生成
物中の主成分が脱水素環化生成物となるに充分な温度お
よび接触時間をもって、８族金属成分含有の活性炭と接
触させることを特徴とするジベンゾフラン類の製法に関
する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing dibenzofurans, and more particularly, the present invention relates to a method for producing dibenzofurans, and more particularly, a method for producing dibenzofurans, in which the main component of the product is a dehydrocyclized product of 2-cyclohexenylcyclohexanone. The present invention relates to a method for producing dibenzofurans, which comprises bringing them into contact with activated carbon containing a Group 8 metal component at a temperature and for a contact time sufficient for the production of dibenzofurans.
（従来の技術）
ジベンゾフランの合成法としては、古くからフェノール
の熱縮合あるいは接触縮合による方法、ビフェニルエー
テルの接触脱水素環化による方法、２−ヒドロキシビフ
ェニルの脱水素環化による方法、２−シクロへキセニル
シクロヘキサノンの酸化脱水素による方法（特開昭５１
−７５０５８号公報）等が知られている。(Prior art) Methods for synthesizing dibenzofuran include a method by thermal condensation or catalytic condensation of phenol, a method by catalytic dehydrocyclization of biphenyl ether, a method by dehydrocyclization of 2-hydroxybiphenyl, and a method by cyclodehydrogenation of 2-hydroxybiphenyl. Method by oxidative dehydrogenation of hexenylcyclohexanone
-75058) and the like are known.
（発明が解決しようとする課題）
しかしながら、公知のフェノールから合成する方法、ジ
フェニルエーテルから合成する方法は、いずれも選択率
が低く、低収率である。２−ヒドロキシビフェニルより
合成する方法は比較的高い収率であるが、高価な原料を
必要とする等問題を有している。また、公知の２−シク
ロヘキセニルシクロヘキサノンより酸化的脱水素により
ベンゾフランを合成する方法は、酸素を反応剤として用
いるため原料の燃焼ロスがさけられない等、公知方法は
いずれも工業的製法としては満足できるレベルにない。(Problems to be Solved by the Invention) However, the known methods of synthesizing from phenol and methods of synthesizing from diphenyl ether have low selectivity and low yield. Although the method of synthesizing from 2-hydroxybiphenyl has a relatively high yield, it has problems such as requiring expensive raw materials. In addition, the known method of synthesizing benzofuran from 2-cyclohexenylcyclohexanone by oxidative dehydrogenation uses oxygen as a reactant, so combustion loss of raw materials cannot be avoided, and all of the known methods are satisfactory as industrial production methods. I'm not at the level where I can do it.
（課題を解決するための手段）
本発明者らは、比較的容易に得られる原料を用い、高選
択率でジベンゾフラン類を製造する方法について鋭意検
討を加えた結果、２−シクロへキシルシクロヘキサノー
ルを脱水素環化生成物が主成分となるに充分な温度およ
び接触時間をもって、８族金属成分含有の活性炭と接触
させることにより、ジベンゾフラン類が高い選択率で製
造できることを見出したものである。(Means for Solving the Problems) As a result of extensive research into a method for producing dibenzofurans with high selectivity using relatively easily obtained raw materials, the present inventors found that 2-cyclohexylcyclohexanol It has been discovered that dibenzofurans can be produced with high selectivity by contacting activated carbon containing a Group 8 metal component at a temperature and for a contact time sufficient to make the dehydrocyclization product the main component.
本発明に用いる原料である２−シクロへキシルシクロヘ
キサノールは、シクロヘキサノン類の酸触媒による脱水
縮合等の方法で容易に得ることができる。２−シクロヘ
キセニルシクロヘキサノン類としては、２−シクロへキ
セニルシクロヘキサノンおよびシクロへキセニル置換基
のβ位が少なくとも未置換のアルキル置換誘導体等が挙
げられる。例えば、２−（ｐ−メチルシクロへキセニル
）４−メチルシクロヘキサノン等を挙げることができる
。さらに、上記原料の部分脱水素／水添生成物も同様に
、本発明使用の原料として用いることができる。これら
の具体例としては、２−シクロへキシルヘキサノン、２
−シクロへキシルシクロヘキサノール、２−シクロへキ
サジェニルシクロヘキサノン等を挙げることができる。2-cyclohexylcyclohexanol, which is a raw material used in the present invention, can be easily obtained by a method such as dehydration condensation of cyclohexanones using an acid catalyst. Examples of the 2-cyclohexenylcyclohexanones include 2-cyclohexenylcyclohexanone and alkyl-substituted derivatives in which at least the β-position of the cyclohexenyl substituent is unsubstituted. For example, 2-(p-methylcyclohexenyl)4-methylcyclohexanone and the like can be mentioned. Additionally, partial dehydrogenation/hydrogenation products of the above raw materials can likewise be used as raw materials for use in the present invention. Specific examples of these include 2-cyclohexylhexanone, 2-cyclohexylhexanone,
-cyclohexylcyclohexanol, 2-cyclohexagenylcyclohexanone, and the like.
本発明に用いる８族金属成分含有の活性炭触媒に用いる
活性炭は、原料による制限はなく、ヤシ殻系、石炭系、
石油ピッチ系、木粉系等いずれのものでもよく、これら
活性炭の比表面積としては、通常３００ポ／ｇ〜１５０
０ボ／ｇ程度のものが好ましい。活性炭含有の８族金属
成分としては、鉄、ニッケル、コバルト、白金、パラジ
ウム、ルテニウム、ロジウム、イリジウム等が挙げられ
る。The activated carbon used in the activated carbon catalyst containing Group 8 metal components used in the present invention is not limited by the raw material, and is coconut shell-based, coal-based,
It may be petroleum pitch-based, wood flour-based, etc., and the specific surface area of these activated carbons is usually 300 po/g to 150 po/g.
Preferably, it has a value of about 0 bo/g. Examples of the Group 8 metal component containing activated carbon include iron, nickel, cobalt, platinum, palladium, ruthenium, rhodium, and iridium.
特に好ましいのはニッケル、白金、パラジウムである。Particularly preferred are nickel, platinum, and palladium.
これら金属成分の含有量としては０．０５〜２０重量％
、好ましくは０．１〜１０重量％である。金属成分の担
持方法としては、公知の含浸法等いずれの方法で行って
もよい。さらに、これら金属成分含有活性炭触媒は、反
応前に通常水素気流中で還元処理して用いられる。The content of these metal components is 0.05 to 20% by weight
, preferably 0.1 to 10% by weight. The metal component may be supported by any known method such as impregnation. Furthermore, these metal component-containing activated carbon catalysts are usually subjected to reduction treatment in a hydrogen stream before use.
本発明における反応条件としては３５０〜５５０°Ｃ１
好ましくは４００〜５００℃の温度、原料供給速度とし
て０．０５〜２の容量時間空間速度（ＬＨ３Ｖ）、好ま
しくは０．１〜１が用いられる。特に好ましいのは、第
１図に示すＡＢＣＤで囲まれた範囲である。さらに、反
応系に窒素等の不活性ガスあるいは水素を希釈剤として
存在させてもよい。特に水素の存在は、触媒の劣化抑制
効果もあり好ましい。水素を供給する際の量としては、
水素／原料のモル比として１〜１０が適当である。The reaction conditions in the present invention are 350 to 550°C1
Preferably, a temperature of 400 to 500 DEG C. and a raw material feed rate of 0.05 to 2, preferably 0.1 to 1, are used. Particularly preferred is the range surrounded by ABCD shown in FIG. Furthermore, an inert gas such as nitrogen or hydrogen may be present as a diluent in the reaction system. In particular, the presence of hydrogen is preferable since it also has the effect of suppressing deterioration of the catalyst. The amount of hydrogen to be supplied is as follows:
A suitable hydrogen/raw material molar ratio is 1 to 10.
反応温度が低くすぎたり、接触時間が短かすぎると、ジ
ベンゾフランの収率、選択率が劣り、反応温度が高すぎ
たり、接触時間が長すぎると、原料の分解生成物が増大
し、ジベンゾフランの選択率が劣る。If the reaction temperature is too low or the contact time is too short, the yield and selectivity of dibenzofuran will be poor; if the reaction temperature is too high or the contact time is too long, the decomposition products of the raw material will increase, and the dibenzofuran will be degraded. Selectivity is poor.
（発明の効果）
本発明の方法によれば、容易に得られる原料よりジベン
ゾフラン類を高選択率、高収率で製造することができる
。酸素等の酸化剤を用いないため、原料の燃焼ロスが発
生しない。(Effects of the Invention) According to the method of the present invention, dibenzofurans can be produced with high selectivity and high yield from easily obtained raw materials. Since no oxidizing agent such as oxygen is used, there is no combustion loss of raw materials.
（実施例）
以下、実施例をあげて本発明を具体的に説明するが、本
発明は、これに限定されるものではない。(Example) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
実施例１
市販の粒状活性炭（ピッツバーグ炭 ＣＡＬ）に硝酸ニ
ッケル８重量％水溶液を含浸させ、次いで１１０℃、４
時間乾燥後、窒素雰囲気中で４５０゛Ｃ１３時間仮焼し
た。この触媒は、ニッケル金属として２重量％含有して
いた。このニッケル含有活性炭５ｇを１５ｍｍφ×３０
０−のステンレス製反応管に充填し、水素気流中で４０
０°Ｃに加熱し、約５時間遠元処理を行った０次いで反
応部を４００″Ｃに加熱し、定量ポンプにより２−シク
ロへキセニルシクロヘキサノンを２． ０ｒｎ１／）ｌ
ｒ （ＬＨ３Ｖ＝０．１８ｈｒ−’） 、水素を１．８
ｊ２／ｌｌｒの速度で供給し、脱水素環化反応を行わせ
た結果、２−シクロへキセニルシクロヘキサノンの転化
率は９９％であり、ジベンゾフランの選択率は５５％で
あった。なお、脱水素中間体として、オルソフェニルフ
ェノールが３２％の選択率で存在していた。Example 1 Commercially available granular activated carbon (Pittsburgh Charcoal CAL) was impregnated with an 8% by weight aqueous solution of nickel nitrate, and then heated at 110°C for 4
After drying for an hour, it was calcined at 450°C for 13 hours in a nitrogen atmosphere. This catalyst contained 2% by weight of nickel metal. 5g of this nickel-containing activated carbon is 15mmφ x 30
Filled in a stainless steel reaction tube with a temperature of
The reaction section was then heated to 400"C and 2.0rn1/)l of 2-cyclohexenylcyclohexanone was heated to 0°C and subjected to a long-distance treatment for about 5 hours.
r (LH3V=0.18hr-'), hydrogen 1.8
As a result of the dehydrogenation cyclization reaction carried out by supplying at a rate of 2/llr, the conversion rate of 2-cyclohexenylcyclohexanone was 99% and the selectivity of dibenzofuran was 55%. Note that orthophenylphenol was present as a dehydrogenation intermediate at a selectivity of 32%.
実施例２
実施例１と同様に、ただし、原料２−シクロへキセニル
シクロヘキサノンの供給量をＬＨ３Ｖとして０．１５ｈ
ｒ−’とし、水素量を原料に対し６モル１モルで供給し
、反応温度４１０°Ｃで反応させた。その結果、２−シ
クロへキセニルシクロヘキサノンの転化率は１００％で
、ジベンゾフランの収率は７５＋ｍｏｌχであった。Example 2 Same as Example 1, except that the feed rate of raw material 2-cyclohexenylcyclohexanone was set to LH3V for 0.15 h.
r-', hydrogen was supplied in an amount of 6 mol 1 mol relative to the raw material, and the reaction was carried out at a reaction temperature of 410°C. As a result, the conversion rate of 2-cyclohexenylcyclohexanone was 100%, and the yield of dibenzofuran was 75+molχ.
実施例３
市販のピッチ系活性炭（呉羽化学製ビーズ炭）に塩化白
金酸水溶液（２０％）を含浸させ、実施例１と同様に処
理し、白金金属として１．５重量％含有の活性炭触媒を
調製した。このものを触媒とし、実施例１と同様に２−
シクロへキセニルシクロヘキサノンの環化脱水素反応を
行った。その結果、２−シクロへキセニルシクロヘキサ
ノンの転化率１００％、ジベンゾフランの収率６０％で
あった。Example 3 Commercially available pitch-based activated carbon (bead charcoal manufactured by Kureha Chemical Co., Ltd.) was impregnated with a chloroplatinic acid aqueous solution (20%) and treated in the same manner as in Example 1, and an activated carbon catalyst containing 1.5% by weight of platinum metal was added. Prepared. Using this as a catalyst, 2-
The cyclodehydrogenation reaction of cyclohexenylcyclohexanone was carried out. As a result, the conversion rate of 2-cyclohexenylcyclohexanone was 100%, and the yield of dibenzofuran was 60%.
実施例４
実施例３と同様に、ただし、ＬＨ３Ｖ＝０．２５ｈｒ−
’とし、反応温度を４５０ ’Ｃおよび５００°Ｃに変
え脱水素環化反応を行った。その結果、それぞれ転化率
１００％、ジベンゾフラン収率８０％、および転化率１
００％、ジベンゾフラン収率６２％であった。Example 4 Same as Example 3, but LH3V=0.25hr-
', and the dehydrocyclization reaction was carried out by changing the reaction temperature to 450'C and 500°C. As a result, the conversion rate was 100%, the dibenzofuran yield was 80%, and the conversion rate was 1.
00%, and the dibenzofuran yield was 62%.
実施例５
実施例１と同様の方法で、原料として２−（ｐ−メチル
シクロへキセニル）４−メチルシクロヘキサノンを用い
、触媒として実施例３で調製の白金含有活性炭触媒を用
い、反応条件は反応温度４２０℃、ＬＨ３Ｖ＝０．２ｈ
ｒ−’、Ｈｔ／原料モル比２で行った。その結果、原料
の転化率１００％、２．６−シメチルベンゾフランの収
率は７６％であった。Example 5 In the same manner as in Example 1, 2-(p-methylcyclohexenyl)4-methylcyclohexanone was used as the raw material, the platinum-containing activated carbon catalyst prepared in Example 3 was used as the catalyst, and the reaction conditions were the reaction temperature. 420℃, LH3V=0.2h
r-', Ht/raw material molar ratio was 2. As a result, the conversion rate of the raw materials was 100%, and the yield of 2,6-dimethylbenzofuran was 76%.
実施例６
実施例５と同様の方法条件で、ただし、原料を２−シク
ロヘキセニルシクロヘキサノンに替え脱水素反応を行っ
た。その結果、２−シクロへキセニルシクロヘキサノン
の転化率は１００％で、ジベンゾフランの収率は７０％
であった。Example 6 A dehydrogenation reaction was carried out under the same method conditions as in Example 5, except that the raw material was changed to 2-cyclohexenylcyclohexanone. As a result, the conversion rate of 2-cyclohexenylcyclohexanone was 100%, and the yield of dibenzofuran was 70%.
Met.
比較例１
実施例３と同様に、ただし、反応温度３５０°Ｃ１ＬＨ
３Ｖ＝０，２５ｈｒ−’、■ｚ／原料原料モル比丘った
。その結果、２−シクロへキセニルシクロヘキサノンの
転化率〜１００％で、ジベンゾフラン収率１５％、脱水
素中間体のオルソフェニルフェノールの収率４０％を示
した。Comparative Example 1 Same as Example 3, but reaction temperature 350°C1LH
3V=0.25hr-', z/raw material molar bhikkhu. As a result, the conversion of 2-cyclohexenylcyclohexanone was ~100%, the yield of dibenzofuran was 15%, and the yield of orthophenylphenol, a dehydrogenation intermediate, was 40%.
比較例２
実施例１と同様に、ただし、反応温度５５０°Ｃで２−
シクロヘキセニルシクロヘキサノンの脱水素反応を行っ
た。その結果、２−シクロへキセニルシクロヘキサノン
の転化率１００％で、分解生成物の選択率６５％、ジベ
ンゾフランの選択率２１％であった。Comparative Example 2 Same as Example 1, except that 2-
A dehydrogenation reaction of cyclohexenylcyclohexanone was carried out. As a result, the conversion rate of 2-cyclohexenylcyclohexanone was 100%, the selectivity of decomposition products was 65%, and the selectivity of dibenzofuran was 21%.
囲を示すグラフである。This is a graph showing the
（ばか１名）(1 idiot)
Claims (1)
物中の主成分が脱水素環化生成物となるに充分な温度お
よび接触時間をもって、８族金属成分含有の活性炭と接
触させることを特徴とするジベンゾフラン類の製法。Dibenzofurans characterized in that 2-cyclohexenylcyclohexanones are brought into contact with activated carbon containing a group 8 metal component at a temperature and for a contact time sufficient for the main component in the dehydrogenation product to become a dehydrogenation cyclization product. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63305999A JP2639576B2 (en) | 1988-12-05 | 1988-12-05 | Manufacturing method of dibenzofurans |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63305999A JP2639576B2 (en) | 1988-12-05 | 1988-12-05 | Manufacturing method of dibenzofurans |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02152973A true JPH02152973A (en) | 1990-06-12 |
| JP2639576B2 JP2639576B2 (en) | 1997-08-13 |
Family
ID=17951852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63305999A Expired - Lifetime JP2639576B2 (en) | 1988-12-05 | 1988-12-05 | Manufacturing method of dibenzofurans |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2639576B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49103897A (en) * | 1973-02-08 | 1974-10-01 | ||
| JPS5175058A (en) * | 1974-11-25 | 1976-06-29 | Anic Spa | |
| JPS624278A (en) * | 1985-06-27 | 1987-01-10 | ヘキスト アクチェンゲゼルシャフト | Production of 2-aminobenzothiazole |
| JPS624442A (en) * | 1985-06-28 | 1987-01-10 | バイエル・アクチエンゲゼルシヤフト | Carrying catalyst, manufacture thereof and usage thereof formanufacturing hydroxyphenyl |
-
1988
- 1988-12-05 JP JP63305999A patent/JP2639576B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49103897A (en) * | 1973-02-08 | 1974-10-01 | ||
| JPS5175058A (en) * | 1974-11-25 | 1976-06-29 | Anic Spa | |
| JPS624278A (en) * | 1985-06-27 | 1987-01-10 | ヘキスト アクチェンゲゼルシャフト | Production of 2-aminobenzothiazole |
| JPS624442A (en) * | 1985-06-28 | 1987-01-10 | バイエル・アクチエンゲゼルシヤフト | Carrying catalyst, manufacture thereof and usage thereof formanufacturing hydroxyphenyl |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2639576B2 (en) | 1997-08-13 |
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