JPS632942A - Production of alkyl, formyltetralin - Google Patents
Production of alkyl, formyltetralinInfo
- Publication number
- JPS632942A JPS632942A JP61145455A JP14545586A JPS632942A JP S632942 A JPS632942 A JP S632942A JP 61145455 A JP61145455 A JP 61145455A JP 14545586 A JP14545586 A JP 14545586A JP S632942 A JPS632942 A JP S632942A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- formyltetralin
- alkyltetralin
- producing
- dicarboxylic acid
- 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.)
- Pending
Links
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- WJRGJANWBCPTLH-UHFFFAOYSA-N 2-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2CC(C)CCC2=C1 WJRGJANWBCPTLH-UHFFFAOYSA-N 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- SJHWXQCUJFXFFP-UHFFFAOYSA-N 2-butyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2CC(CCCC)CCC2=C1 SJHWXQCUJFXFFP-UHFFFAOYSA-N 0.000 claims abstract description 3
- JUANVGODPSRCGD-UHFFFAOYSA-N 2-ethyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2CC(CC)CCC2=C1 JUANVGODPSRCGD-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZEHICBNVEHBNRK-UHFFFAOYSA-N 2-propan-2-yl-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2CC(C(C)C)CCC2=C1 ZEHICBNVEHBNRK-UHFFFAOYSA-N 0.000 claims abstract description 3
- IVIDJLLPQYHHLM-UHFFFAOYSA-N 6-methyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(C)=CC=C21 IVIDJLLPQYHHLM-UHFFFAOYSA-N 0.000 claims description 4
- OOPPKRUACFCVFK-UHFFFAOYSA-N 6-butyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(CCCC)=CC=C21 OOPPKRUACFCVFK-UHFFFAOYSA-N 0.000 claims description 2
- DLHGUEXPTGUBGR-UHFFFAOYSA-N 6-ethyl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(CC)=CC=C21 DLHGUEXPTGUBGR-UHFFFAOYSA-N 0.000 claims description 2
- OKJDRCDBHNDGRV-UHFFFAOYSA-N 6-propan-2-yl-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(C(C)C)=CC=C21 OKJDRCDBHNDGRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- NYNSNUNMTUNAEO-UHFFFAOYSA-N 5,6,7,8-tetrahydronaphthalene-2-carbaldehyde Chemical compound C1CCCC2=CC(C=O)=CC=C21 NYNSNUNMTUNAEO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 abstract 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetraline Natural products C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 9
- 229910002090 carbon oxide Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 6
- -1 alkenyl aromatic hydrocarbons Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WQXDRWLUNDERNE-UHFFFAOYSA-N 1-(1,2,3,4-tetrahydronaphthalen-2-yl)ethanone Chemical compound C1=CC=C2CC(C(=O)C)CCC2=C1 WQXDRWLUNDERNE-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 2
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000022244 formylation Effects 0.000 description 2
- 238000006170 formylation reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEPUKHYQNXSSKV-UHFFFAOYSA-N 1-(5,6,7,8-tetrahydronaphthalen-2-yl)ethanone Chemical compound C1CCCC2=CC(C(=O)C)=CC=C21 VEPUKHYQNXSSKV-UHFFFAOYSA-N 0.000 description 1
- WWGUMAYGTYQSGA-UHFFFAOYSA-N 2,3-dimethylnaphthalene Chemical compound C1=CC=C2C=C(C)C(C)=CC2=C1 WWGUMAYGTYQSGA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- Catalysts (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
この発明は、２−アルキルテトラリンから２−アルキル
、６または７−ホルミルテトラリンを、６−アルキルテ
トラリンから６−アルキル、７−ホルミルテトラリンを
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a method for producing 2-alkyl, 6 or 7-formyltetralin from 2-alkyltetralin and 6-alkyl, 7-formyltetralin from 6-alkyltetralin. Regarding.
従来技術
２−アルキル、６−ホルミルテトラリンは、脱水素およ
び酸化することにより容易に２，６−ナフタレンジカル
ボン酸に変化させることができる２、６−ナフタレンジ
カルボン酸は、有用な高分子合成原料であり、例えばこ
れから導かれるポリエステルは、テレフタル酸を原料と
するポリエステルに比へ、特に機械的強度、耐熱性、寸
法安定性など種々の点で優れたフィルムや各種成型物を
与えることが知られており、２．６−ナフタレンジカル
ボン酸の安価な工業的製法の開発が強く望まれていた。Prior Art 2-Alkyl, 6-formyltetralin can be easily converted into 2,6-naphthalene dicarboxylic acid by dehydrogenation and oxidation. 2,6-naphthalene dicarboxylic acid is a useful raw material for polymer synthesis. For example, the polyester derived from this is known to provide films and various molded products that are superior in various aspects, such as mechanical strength, heat resistance, and dimensional stability, compared to polyesters made from terephthalic acid. Therefore, there has been a strong desire to develop an inexpensive industrial method for producing 2,6-naphthalene dicarboxylic acid.
また、６−アルキル、７−ホルミルテトラリンは、脱水
素および酸化することにより容易に６゜７ （２，３）
−ナフタレンジカルボン酸に変化させることができる。In addition, 6-alkyl, 7-formyltetralin can be easily converted to 6°7 (2,3) by dehydrogenation and oxidation.
- Can be converted to naphthalene dicarboxylic acid.
６，７−ナフタレンジカルボン酸は、有用な高分子合成
原料になり得ると予想されるため、６，７−ホルミルテ
トラリンの安価な工業的製造法の開発が強く望まれてい
る。Since 6,7-naphthalene dicarboxylic acid is expected to be a useful raw material for polymer synthesis, there is a strong desire to develop an inexpensive industrial production method for 6,7-formyltetralin.
従来、ナフタレンジカルボン酸は、ジメチルナフタレン
あるいはジイソプロピルナフタレンの酸化により得られ
ている。例えば２，６−ジメチルナフタレンは、酸化す
ることにより容易に２，６−ナフタレンジカルボン酸に
することができる。Conventionally, naphthalene dicarboxylic acid has been obtained by oxidizing dimethylnaphthalene or diisopropylnaphthalene. For example, 2,6-dimethylnaphthalene can be easily converted into 2,6-naphthalene dicarboxylic acid by oxidation.
ナフタレンをメチル化すると、−般にモノ体からポリ体
の混合物が得られ、その中のジメチル体も殆どすべての
異性体が生成するため、所定位置にアルキル基を有する
目的とする２、６−体、２゜７−体、６，７−体の選択
率はいずれも低く、工業的生産は、特定の経済的条件、
例えば副生ずる生成物が有利に活用できる等の条件がな
ければ成立し得ない。When naphthalene is methylated, a mixture of mono- to poly-isomers is generally obtained, and almost all of the dimethyl isomers are produced. The selectivity of the isomers, 2゜7-isomers, and 6,7-isomers are all low, and industrial production is difficult under certain economic conditions.
For example, this cannot be achieved unless there are conditions such as by-products being able to be used advantageously.
さらにナフタレンとプロピレンから製造されるジイソプ
ロピルナフタレンは、比較的容易に２゜６−体が分離で
きるが、これを分子状酸素によって公知の触媒の存在下
酸化し、２，６−ナフタレンジカルボン酸を高収率で製
造することは非常に困難であった。Furthermore, diisopropylnaphthalene produced from naphthalene and propylene can be relatively easily separated into its 2-6-isomer, which is oxidized with molecular oxygen in the presence of a known catalyst to produce 2,6-naphthalene dicarboxylic acid. It was very difficult to produce with high yield.
一方、単環芳香族炭化水素とジエン系炭化水素とからア
ルケニル芳香族炭化水素を合成し、これの環化脱水素な
どによりジアルキルナフタレンを製造する方法も提案さ
れているが、この方法は、多数の反応工程を必要とし、
製造コストが高く、工業的製法としては適当でない。On the other hand, a method has also been proposed in which alkenyl aromatic hydrocarbons are synthesized from monocyclic aromatic hydrocarbons and diene hydrocarbons, and dialkylnaphthalenes are produced by cyclodehydrogenation, etc.; Requires a reaction step of
The manufacturing cost is high and it is not suitable as an industrial manufacturing method.
上記とは別に、２−アルキルナフタレンをＡ２Ｃ１ｚを
触媒として、ニトロベンゼン中で酸塩化物、酸無水物な
どでアシル化することにより２−アルキル、６−アシル
ナフタレンが得られることも知られている（米国特許第
３２３４２８６ ）。Apart from the above, it is also known that 2-alkyl, 6-acylnaphthalenes can be obtained by acylating 2-alkylnaphthalenes with acid chlorides, acid anhydrides, etc. in nitrobenzene using A2C1z as a catalyst ( U.S. Pat. No. 3,234,286).
また、６，７−ナフタレンジカルボン酸は、６．７ （
２，３）−ジメチルナフタレンを酸化することにより容
易に６，７−ナフタレンジカルボン酸にすることができ
るが、ナフタレンをメチル化して６，７−ジメチルナフ
タレンを高選択率、高収率で得ることは困難である。In addition, 6,7-naphthalene dicarboxylic acid is 6.7 (
6,7-naphthalene dicarboxylic acid can be easily obtained by oxidizing 2,3)-dimethylnaphthalene, but 6,7-dimethylnaphthalene can be obtained with high selectivity and yield by methylating naphthalene. It is difficult.
しかしながら、２−アルキルテトラリンを酸触媒の存在
下、−酸化炭素と反応させ、２−アルキル、６または７
−ホルミルテトラリンを製造する方法、および６−アル
キルテトラリンを酸触媒の存在下、−酸化炭素と反応さ
せ、６−アルキル。However, when 2-alkyl tetralin is reacted with -carbon oxide in the presence of an acid catalyst, 2-alkyl, 6 or 7
- A method for producing formyltetralin, and reacting 6-alkyltetralin with -carbon oxide in the presence of an acid catalyst to produce 6-alkyltetralin.
７−ホルミルテトラリンを製造する方法は、現在のとこ
ろ提案されていない。No method for producing 7-formyltetralin has been proposed at present.
解決しようとする問題点
この発明は、脱水素および酸化することにより容易に２
．６−ナフタレンジカルボン酸または６．７−ナフタレ
ンジカルボン酸に変化させることができる２−アルキル
、６または７−ホルミルテトラリンあるいは６−アルキ
ル、７−ホルミルテトラリンの製造方法を提供するもの
である。Problems to be Solved This invention can easily solve the problem by dehydrogenation and oxidation.
．． The present invention provides a method for producing 2-alkyl, 6- or 7-formyltetralin or 6-alkyl, 7-formyltetralin that can be converted into 6-naphthalene dicarboxylic acid or 6.7-naphthalene dicarboxylic acid.
発明の詳細
この発明は、２−アルキルテトラリンおよび／または６
−アルキルテトラリンと一酸化炭素とを、酸触媒の存在
下、反応せしめることを特徴とするアルキル、ホルミル
テトラリンの゛製造方法である。DETAILS OF THE INVENTION This invention provides 2-alkyl tetralin and/or 6
- A method for producing alkyl and formyltetralin, which comprises reacting an alkyltetralin and carbon monoxide in the presence of an acid catalyst.
本発明における反応は、通常加圧容器を使用し、必要に
応じて窒素のような不活性ガスで置換したのち、２−ア
ルキルテトラリンまたは６−アルキルテトラリンを仕込
み、ＨＦとＢＦｘを導入したのち、−酸化炭素を圧入し
て撹拌等の手段により気液接触を十分行いながら実施す
る。In the reaction in the present invention, a pressurized container is usually used, and after purging with an inert gas such as nitrogen as necessary, 2-alkyltetralin or 6-alkyltetralin is charged, HF and BFx are introduced, and then, - Carbon oxide is injected under pressure and carried out while sufficient gas-liquid contact is made by means such as stirring.
本発明の方法における出発原料である２−アルキルテト
ラリンとしては、２−メチルテトラリン、２−エチルテ
トラリン、２−イソプロピルテトラリン、２−ブチルテ
トラリンが用いられる。また、６−アルキルテトラリン
としては、６−メチルテトラリン、６−エチルテトラリ
ン、６−イソプロピルテトラリン、６−ブチルテトラリ
ンを用いる。As the 2-alkyltetralin which is a starting material in the method of the present invention, 2-methyltetralin, 2-ethyltetralin, 2-isopropyltetralin, and 2-butyltetralin are used. Further, as the 6-alkyltetralin, 6-methyltetralin, 6-ethyltetralin, 6-isopropyltetralin, and 6-butyltetralin are used.
酸触媒としては、ＨＦＢＦ３、ＣＦ ３ Ｓ Ｏ３Ｈ，
ＡＱＣ９ｚ ＨＣＩ、Ａ Ｉ Ｂ ｒ ３− ＨＢ
ｒ 。As acid catalysts, HFBF3, CF3SO3H,
AQC9z HCI, A I B r 3-HB
r.
ＳｂＦ、−ＨＦを用いることができるが、経済的見地か
ら、反応終了後酸触媒を回収して循環使用する必要があ
るが、この点からすればＨＦ−ＢＦが有利である。Although SbF and -HF can be used, from an economical point of view, it is necessary to recover the acid catalyst after the reaction is completed and recycle it, and from this point of view, HF-BF is advantageous.
ＨＦの使用量は、用いるアルキルテトラリンに対して、
０．５〜１００倍モル、好ましくは１．５〜５倍モルで
ある。ＢＦｆｆは、１．０〜１０倍モル、好ましくは１
．５〜５倍モルである。The amount of HF used is based on the alkyl tetralin used.
It is 0.5 to 100 times the mole, preferably 1.5 to 5 times the mole. BFff is 1.0 to 10 times the mole, preferably 1
．． It is 5 to 5 times the mole.
反応温度は特に限定する必要がなく、常温で十分である
。−酸化炭素圧力は３〜５０ ｋｇ／ ｃｎｔ Ｇ、好
ましくは５〜１０ｋｇ／ｄＧである。また、−酸化炭素
としては、例えば水性ガスのようなものを使用すること
もできるが、純粋な一酸化炭素を使用するのが好ましい
。The reaction temperature does not need to be particularly limited, and room temperature is sufficient. - The carbon oxide pressure is between 3 and 50 kg/cnt G, preferably between 5 and 10 kg/dG. Further, as the carbon oxide, for example, water gas can be used, but it is preferable to use pure carbon monoxide.
本発明の原料である２または６−アルキルテトラリンの
場合は、ホルミル基（−ｃｒｒｏ）の入る位置は４ケ所
と予想されるため、他の異性体の生成が懸念されたが、
２または６−アルキルホルミルテトラワンの収率は、７
０％以上で、しかも驚くべきことに２−アルキル、６ま
たは７−ホルミルチトラリンを９４％以上、６−アルキ
ル、７−ホルミルチトラリンを９７％以上の高選択率で
製造することができる。ただし、ここでいう選択率とは
、生成アルキルホルミルテト・ラリン中の２゜６−体ま
たは２，７−体、あるいは６，７−体の含有率をいう。In the case of 2- or 6-alkyltetralin, which is the raw material of the present invention, there are expected to be four positions for the formyl group (-crro), so there was a concern that other isomers would be formed.
The yield of 2 or 6-alkylformyltetrawane is 7
0% or more, and surprisingly, it is possible to produce 2-alkyl, 6 or 7-formyltitraline with a high selectivity of 94% or more and 6-alkyl, 7-formyltitraline with a high selectivity of 97% or more. However, the selectivity here refers to the content of 2°6-isomer, 2,7-isomer, or 6,7-isomer in the produced alkylformyltetralin.
この理由は明らかではないが、この反応は一般に親電子
置換反応と考えられており、メチル基等の電子供与基が
付加している場合、オルソ、パラ位配向性であるが、こ
の系でのトルエンのホルミル化においては、パラ位が９
７％、オルソ位が３％となり、パラ位の反応性が非常に
高い。この理由として、反応試薬が大きな立体構造をと
っているためと考えられる。これらのことから２−メチ
ルテトラリンのホルミル化を考えた場合、９．１０位に
アルキル基が付加していると考えれば９位から見ればパ
ラ位は６位、１０位から見ればパラ位は７位となり、６
および７位の反応性が高いためと考える。６−アルキル
テトラリンの場合も同様な理由により、７位の反応性が
高いためと考えるまた、生成した２−アルキル、６およ
び７−ホルミルチトラリンより公知の方法によって容易
に２−アルキル、６ホルミルテトラリンを分離できるの
で、２，６−ナフタレンジカルボン酸の製造方法の有効
な手段となる。同様に６−アルキル。The reason for this is not clear, but this reaction is generally considered to be an electrophilic substitution reaction, and when an electron-donating group such as a methyl group is added, the orientation is in the ortho and para positions. In toluene formylation, the para position is 9.
7%, and 3% for the ortho position, and the reactivity at the para position is extremely high. The reason for this is thought to be that the reaction reagent has a large three-dimensional structure. Considering the formylation of 2-methyltetralin from these points, if we consider that an alkyl group is added to the 9-10th position, the para-position is the 6th-position when viewed from the 9th-position, and the para-position is the 6th-position when viewed from the 10th-position. 7th place, 6
This is thought to be due to the high reactivity of the 7th position. In the case of 6-alkyltetralin, it is believed that this is due to the high reactivity at the 7-position for the same reason.Also, the produced 2-alkyl, 6- and 7-formyltitralin can be easily converted to 2-alkyl, 6-formyl by a known method. Since tetralin can be separated, it is an effective method for producing 2,6-naphthalene dicarboxylic acid. Similarly, 6-alkyl.
７−ホルミルチトラリンは、６，７−ナフタレンジカル
ボン酸の製造原料として有用であり、有効な６−アルキ
ル、７−ホルミルチトラリンの製造方法である。7-formylcitraline is useful as a raw material for producing 6,7-naphthalene dicarboxylic acid, and is an effective method for producing 6-alkyl, 7-formylcitraline.
実施例１
撹拌機付き１００ｍ１のステンレス製オートクレーブに
２−メチルテトラリン１８．７ミリモルを仕込み、氷水
中で冷却しながら減圧した。これをドライアイス−メタ
ノール溶液にて採取した液状のＨＦ２モルを吸引導入し
たのち、ＢＦ３をガス状で８６．５ミリモル撹拌しなが
ら供給した。Example 1 18.7 mmol of 2-methyltetralin was charged into a 100 ml stainless steel autoclave equipped with a stirrer, and the pressure was reduced while cooling in ice water. After 2 mol of liquid HF collected in a dry ice-methanol solution was introduced by suction, 86.5 mmol of BF3 in gaseous form was supplied while stirring.
その後−酸化炭素を撹拌しながら５０ ｋｇ／ ｃａ
Ｇまで供給し、撹拌下θ℃に保ちながら２時間反応せし
めた。反応終了後、反応液を氷水中に採取し、ベンゼン
１００ｍ１にて抽出後、ベンゼン溶液としてアルデヒド
はオキシム化法にて分析し、選択率はガスクロマトグラ
フィーの面積百分率として求めた。Then - 50 kg/ca with stirring of carbon oxide
The mixture was fed up to G and allowed to react for 2 hours while stirring and maintaining the temperature at θ°C. After the reaction was completed, the reaction solution was collected in ice water and extracted with 100 ml of benzene.The benzene solution was analyzed for aldehyde by the oxime conversion method, and the selectivity was determined as an area percentage by gas chromatography.
その結果２−メチルホルミルテトラリンの収率は、９９
．１％で、２−メチル、６または７−ホルミルチトラリ
ンの選択率は９７．６％、未反応の２−メチルテトラリ
ンは０％であった。As a result, the yield of 2-methylformyltetralin was 99
．． At 1%, the selectivity for 2-methyl, 6 or 7-formyltitraline was 97.6%, and unreacted 2-methyltetraline was 0%.
実施例２〜６
実施例１と同様の操作で、反応条件を変更して２−メチ
ルホルミルテトラリンの製造を行った。Examples 2 to 6 2-Methylformyltetralin was produced in the same manner as in Example 1 by changing the reaction conditions.
その結果を実施例１の結果と共に第１表に示す。The results are shown in Table 1 together with the results of Example 1.
なお、実施例５および６については、反応系の圧力が降
下するに従い、随時−酸化炭素を充填し、初期の圧力を
保持するよう努めた。In Examples 5 and 6, as the pressure of the reaction system decreased, carbon oxide was filled as needed to maintain the initial pressure.
第１表に示すとおり、２−メチルホルミルテトラリンの
収率はいずれも７０％以上であり、しかも、２−メチル
、６および７−ホルミルチトラリンの選択率は、いずれ
も９４％以上である。As shown in Table 1, the yield of 2-methylformyltetraline is 70% or more, and the selectivity of 2-methyl, 6, and 7-formyltitraline is 94% or more.
このことは、２−アルキル、６および７−ホルミルチト
ラリンの製造方法として非常に優れた方法であることを
示すものである。This shows that this is an extremely excellent method for producing 2-alkyl, 6- and 7-formyltitraline.
実施例７，８
実施例１と同様の操作で、反応条件を変更して６−メチ
ル、７−ホルミルチトラリンーを製造した。実施例８に
おいては、前記実施例５，６と同様に反応系の圧力が低
下すると一酸化炭素を充填し、初期圧力に保持するよう
努めた。その結果を第２表に示す。Examples 7 and 8 6-Methyl, 7-formyltitraline was produced in the same manner as in Example 1 by changing the reaction conditions. In Example 8, as in Examples 5 and 6, when the pressure of the reaction system decreased, carbon monoxide was charged to maintain the initial pressure. The results are shown in Table 2.
第２表に示すとおり、６−メチルホルミルテトラリンの
収率はいずれも７５％以上であり、６−メチル、７−ホ
ルミルチトラリンの選択率は、９４％以上であった。As shown in Table 2, the yield of 6-methylformyltetraline was 75% or more, and the selectivity of 6-methyl and 7-formyltitraline was 94% or more.
＞叉下会白＞Change meeting white
Claims (4)
キルテトラリンと一酸化炭素とを、酸触媒の存在下、反
応せしめることを特徴とするアルキルホルミルルテトラ
リンの製造方法。(1) A method for producing alkylformyltetralin, which comprises reacting 2-alkyltetralin and/or 6-alkyltetralin with carbon monoxide in the presence of an acid catalyst.
、２−エチルテトラリン、２−イソプロピルテトラリン
、２−ブチルテトラリンである特許請求の範囲第１項記
載のアルキル、ホルミルテトラリンの製造方法。(2) The method for producing alkyl, formyltetralin according to claim 1, wherein the 2-alkyltetralin is 2-methyltetralin, 2-ethyltetralin, 2-isopropyltetralin, or 2-butyltetralin.
、６−エチルテトラリン、６−イソプロピルテトラリン
、６−ブチルテトラリンである特許請求の範囲第１項記
載のアルキル、ホルミルテトラリンの製造方法。(3) The method for producing alkyl, formyltetralin according to claim 1, wherein the 6-alkyltetralin is 6-methyltetralin, 6-ethyltetralin, 6-isopropyltetralin, or 6-butyltetralin.
Ｈ、ＡｌＣｌ＿３−ＨＣｌ、ＡｌＢｒ＿３−ＨＢｒ、Ｓ
ｂＦ＿５−ＨＦのいずれかを用いる特許請求の範囲第１
項記載のアルキル、ホルミルテトラリンの製造方法。(4) HF-BF_3, CF_3SO_3 as acid catalysts
H, AlCl_3-HCl, AlBr_3-HBr, S
Claim 1 using either bF_5-HF
The method for producing alkyl and formyltetralin described in Section 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61145455A JPS632942A (en) | 1986-06-20 | 1986-06-20 | Production of alkyl, formyltetralin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61145455A JPS632942A (en) | 1986-06-20 | 1986-06-20 | Production of alkyl, formyltetralin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS632942A true JPS632942A (en) | 1988-01-07 |
Family
ID=15385626
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61145455A Pending JPS632942A (en) | 1986-06-20 | 1986-06-20 | Production of alkyl, formyltetralin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS632942A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5012007A (en) * | 1989-10-05 | 1991-04-30 | Varadaraj Elango | Method for producing 1-indanone derivatives |
-
1986
- 1986-06-20 JP JP61145455A patent/JPS632942A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5012007A (en) * | 1989-10-05 | 1991-04-30 | Varadaraj Elango | Method for producing 1-indanone derivatives |
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