JPH03190868A - Production of coumaran - Google Patents
Production of coumaranInfo
- Publication number
- JPH03190868A JPH03190868A JP1330188A JP33018889A JPH03190868A JP H03190868 A JPH03190868 A JP H03190868A JP 1330188 A JP1330188 A JP 1330188A JP 33018889 A JP33018889 A JP 33018889A JP H03190868 A JPH03190868 A JP H03190868A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- condensed ring
- reaction
- alkyl group
- aldehyde
- 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
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 4
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 3
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003377 acid catalyst Substances 0.000 abstract 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- -1 boron trifluoride ether salt Chemical class 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- FTZILAQGHINQQR-UHFFFAOYSA-N 2-Methylpentanal Chemical compound CCCC(C)C=O FTZILAQGHINQQR-UHFFFAOYSA-N 0.000 description 2
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 2
- BYGQBDHUGHBGMD-UHFFFAOYSA-N 2-methylbutanal Chemical compound CCC(C)C=O BYGQBDHUGHBGMD-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000001893 (2R)-2-methylbutanal Substances 0.000 description 1
- BHVGMUDWABJNRC-UHFFFAOYSA-N (±)-2-methylhexanal Chemical compound CCCCC(C)C=O BHVGMUDWABJNRC-UHFFFAOYSA-N 0.000 description 1
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical group OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical class OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- BWCJVGMZEQDOMY-UHFFFAOYSA-N 2-methyl-2,3-dihydro-1-benzofuran Chemical class C1=CC=C2OC(C)CC2=C1 BWCJVGMZEQDOMY-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 1
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 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
- Furan Compounds (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、クマラン類詳しくは２，３−ジヒドロベンゾ
フラン類の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing coumarans, particularly 2,3-dihydrobenzofurans.
従来のクマラン類の製造法については、たとえば次式の
ような０−オキシ−β−ハロエチルベンゼル誘導体をア
ルカリによシクマラン誘導体に閉環する方法（Ｂｅｒ、
、 ３４．１．８０６ （１９０１）が知られている。Conventional methods for producing coumarans include, for example, a method of ring-closing an 0-oxy-β-haloethylbenzel derivative into a cycloumaran derivative using an alkali (Ber,
, 34.1.806 (1901) is known.
（ここで、 Ｒ’は炭素数２〜８のアルキル基、几２は
また、次式のようなアリルフェノールの０１ａｉｓｅｎ
転位によって得られる０−アリルフェノール類の閉環に
よって、２−メチルクマラン誘導体を合成できる。（Ｊ
、 Ｉｎｄｉａｎ Ｏｈｅｍ、 Ｓｏｃ、、 ３０．３
５５ （１９５３）。(Here, R' is an alkyl group having 2 to 8 carbon atoms, and 2 is also an allylphenol group as shown in the following formula.
2-Methylcoumaran derivatives can be synthesized by ring closure of O-allylphenols obtained by rearrangement. (J
, Indian Ohem, Soc,, 30.3
55 (1953).
Ｊ、 Ｏｒｇ、 Ｏｈｅｍ、、 ５．２１２ （１９４
０） ）高選択的にクマラン類を合成することに成功し
た。J, Org, Ohem, 5.212 (194
0)) We succeeded in synthesizing coumarans with high selectivity.
すなわち、本発明は上記記載で明らかなごとく、−工程
でクマラン類を製造する方法を提供することを目的とす
るものである。That is, as is clear from the above description, an object of the present invention is to provide a method for producing coumarans in -steps.
本発明のクマラン類の製造法は、一般式％式％（１）
で表わされるアルデヒドと、一般式
しかし、これらのクマラン類の合成法はフェノール類か
ら２ないし３段階の工程が必要であシ、工業的にも充分
な収率で合成ができない。The method for producing coumarans of the present invention involves using an aldehyde represented by the general formula % (1) and the general formula %. However, it cannot be synthesized with a sufficient yield industrially.
本発明者らは、これらの問題点について鋭意研究を重ね
た結果、従来のクマラン合成法とは全く異なった方法、
すなわちアルデヒドから１工程でで表わされる芳香族化
合物およびその縮合環とを、モル比０．１：１〜１０：
１、好ましくは１：１〜３：１で酸性触媒下、液相で反
応させ、一般式で表わされる２、３−ジヒドロベンゾフ
ラン類を生成イ名ことを特徴とする。As a result of extensive research into these problems, the present inventors have developed a method that is completely different from the conventional coumaran synthesis method.
That is, in one step from the aldehyde, the aromatic compound represented by and the condensed ring thereof are mixed in a molar ratio of 0.1:1 to 10:
1, preferably 1:1 to 3:1, under an acidic catalyst in a liquid phase to produce 2,3-dihydrobenzofurans represented by the general formula.
（ここで、Ｒ１は炭素数２〜８のアルキル基、Ｖは炭素
数１〜６のアルキル基、Ｂ８は水素原子もしくは芳香族
環に任意の位置に置換されたアルキル基および縮合環、
ｎは１〜３の整数値を示す）本発明に使用される触媒は
、パラトルエンスルフォン酸、塩化第二錫、塩化亜鉛、
塩化アルミニウム、塩化第二鉄、三弗化ホウ素エーテル
塩などがあげられる。これらの触媒にそれぞれ単独で使
用しても本発明の製造法は達成されるが、よシ好ましく
はパラトルエンスルフォン酸を使用するとと、さらに好
ましい使用方法はパラトルエンスルフォン酸と塩化第二
錫などの他の酸性触媒と併用することである。(Here, R1 is an alkyl group having 2 to 8 carbon atoms, V is an alkyl group having 1 to 6 carbon atoms, B8 is a hydrogen atom or an alkyl group substituted at any position on an aromatic ring, and a fused ring,
(n represents an integer value of 1 to 3) The catalyst used in the present invention includes para-toluenesulfonic acid, stannic chloride, zinc chloride,
Examples include aluminum chloride, ferric chloride, and boron trifluoride ether salt. Although the production method of the present invention can be achieved even if each of these catalysts is used alone, it is more preferable to use para-toluenesulfonic acid, and even more preferably to use para-toluenesulfonic acid and stannic chloride. It is to be used in combination with other acidic catalysts.
本発明に使用するフェノール類は、フェノール、クレゾ
ール、レゾルシン、カテコール、ハイドロキノン、ナフ
トール、チモール、ウルシオール、ピロガロール、フロ
ログルシノール等をあげるととができる。Examples of the phenols used in the present invention include phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, thymol, urushiol, pyrogallol, and phloroglucinol.
本発明に使用されるアルデヒドは２−エチルへキサナー
ル、２−エタルブタナール、２−メチルバレルアルデヒ
ド、２−メチルヘキサナール、２−メチルブタナール等
α位にアルキル置換基を有する高級アルデヒドをあげる
ことができる。The aldehydes used in the present invention include higher aldehydes having an alkyl substituent at the α-position, such as 2-ethylhexanal, 2-ethalbutanal, 2-methylvaleraldehyde, 2-methylhexanal, and 2-methylbutanal. .
本発明の製造法におけるアルデヒドとフェノール類との
モル比は０．１：１〜１０：１．好ましくは１：１〜３
：１である。The molar ratio of aldehyde and phenol in the production method of the present invention is 0.1:1 to 10:1. Preferably 1:1-3
:1.
触媒の使用量はアルデヒドに対して０．０１〜１０重量
係、好ましくは０．０５〜２重量係が適当である。The appropriate amount of the catalyst to be used is 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on the aldehyde.
本発明の反応温度は原料によシ異なるが、いずれも原料
のリフラックス状態で連続的に生成水を抜き出すことに
よシ反応は進行する。特定の共沸溶媒などを使用する必
要はないが、その使用を妨げるものではない。The reaction temperature of the present invention varies depending on the raw materials, but in all cases the reaction proceeds by continuously extracting produced water while the raw materials are in a reflux state. Although it is not necessary to use a specific azeotropic solvent, this does not preclude its use.
また反応圧力は、反応系が液相であれば常圧、減圧、加
圧のいずれで行ってもよいが通常、操作の容易な常圧反
応で充分である。The reaction pressure may be normal pressure, reduced pressure, or increased pressure as long as the reaction system is in a liquid phase, but normal pressure reaction is usually sufficient since it is easy to operate.
本発明の製造法は、カルボニル基のα位にアルキル置換
基を有するアルデヒドとフェノール類と＝６
を酸性触媒下、−工程でクマラン類を生成するがその反
応は次式に示すような反応工程で進行しているものと考
えられる。In the production method of the present invention, an aldehyde having an alkyl substituent at the α-position of the carbonyl group and a phenol = 6 are mixed under an acidic catalyst to produce coumarans in the - step, and the reaction is carried out in the reaction step shown in the following formula It is thought that this is progressing.
（中間体１）
すなわち、アセタールを生成せずにアルケニルエーテル
を中間体として０１ａｉｓｅｎ転位（アリル転位）に似
た、全く新規な転位反応（ビニル転位）によ＃）ｏ−ビ
ニルフェノール類を生成し、その閉環によってクマラン
類が合成されていると思われる。この際に中間体として
生成する０−アルケニルフェノール（中間体２）はさら
に原料のアルデヒドと反応することが考えられるが、本
発明の製法はこの段階で即座に閉環反応しクマランを生
成する。この閉環反応にはｐ−１ルエンスルフオン酸が
有効にはたらくものと考えられ、触媒としてｐ−）ルエ
ンスルフオン酸を使用した場合クマラン生成の選択率は
高い。(Intermediate 1) That is, o-vinylphenols are produced by a completely new rearrangement reaction (vinyl rearrangement) similar to the 01aisen rearrangement (allyl rearrangement) using an alkenyl ether as an intermediate without generating an acetal. It is thought that coumarans are synthesized by the ring closure. It is conceivable that the 0-alkenylphenol (intermediate 2) produced as an intermediate at this time further reacts with the aldehyde as a raw material, but in the production method of the present invention, a ring-closing reaction occurs immediately at this stage to produce coumaran. It is believed that p-1 toluenesulfonic acid works effectively in this ring-closing reaction, and when p-1 toluenesulfonic acid is used as a catalyst, the selectivity for producing coumaran is high.
本発明はクマラン類を、工業的にも入手の容易なアルデ
ヒドとフェノール類を原料として、全く新規な合成法に
よシー工程で高選択的に合成するものであり、工業的に
もすぐれた方法である。The present invention is a method for highly selectively synthesizing coumarans in a searing process using industrially easily available aldehydes and phenols as raw materials using a completely new synthesis method, and is an excellent method from an industrial perspective. It is.
以下実施例にて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例１
２−エチルブタナール；６０重量部、ｐ−クレゾール；
５３重量部、塩化第二錫；０．１重量部を４つ目フラス
コに仕込み撹拌しながら常圧、リフラックス状態で加熱
を行い、連続的に生成水を抜き出しながら、１５時間保
持し反応を行いせしめたところ、ｐ−クレゾールの反応
率は８３％、２−ジエチル−５−メチルクマランの生成
の選択率は４３．５％であった。Example 1 2-ethylbutanal; 60 parts by weight, p-cresol;
53 parts by weight, 0.1 part by weight of stannic chloride were placed in a fourth flask and heated under normal pressure and reflux while stirring, and held for 15 hours while continuously drawing out the produced water to allow the reaction to proceed. When carried out, the reaction rate of p-cresol was 83%, and the selectivity for production of 2-diethyl-5-methylcoumaran was 43.5%.
実施例２
２−エチルヘキサナール；３０７重量部、ｐクレゾール
；２１６重量部、塩化第二錫；０，２重量部、ｐ −ト
ルエンスルフォン酸；ｏ、ｓ重量部全実施例１と同様の
操作で３時間保持し反応を行いせしめたところ、ｐ−ク
レゾールの反応率は９０係、２−エチルメチル−５−メ
チルクマランの生成の選択率は９２．５％であった。Example 2 2-ethylhexanal; 307 parts by weight, p-cresol; 216 parts by weight, stannic chloride; 0.2 parts by weight, p-toluenesulfonic acid; o, s parts by weight. All in the same manner as in Example 1. When the reaction was carried out by holding for 3 hours, the reaction rate of p-cresol was 90%, and the selectivity for production of 2-ethylmethyl-5-methylcoumaran was 92.5%.
実施例３
２−エチルブタナール：６０重量部、ｐ−クレゾール；
５３重葉部、塩化第二錫：０．１重量部、Ｐ−）ルエン
スルフオン酸；０，４重量部を実施例１と同様の操作で
３時間保持し反応を行いせしめたところ、ｐ−りｌ／ゾ
ールの反応率は８５％、２−ジエチル−５−メチルクマ
ランの生成の選択率は９４．０％でありｔ−６
以上Example 3 2-ethylbutanal: 60 parts by weight, p-cresol;
53 parts by weight, 0.1 parts by weight of stannic chloride, 0.4 parts by weight of P-)luenesulfonic acid were kept in the same manner as in Example 1 for 3 hours to carry out the reaction. The reaction rate of l/sol was 85%, and the selectivity for the production of 2-diethyl-5-methylcoumaran was 94.0%, which was t-6 or higher.
Claims (1)
・・・・・（１）で表わされるアルデヒドと一般式 ▲数式、化学式、表等があります▼・・・・・・・・・
・・・・・（２）で表わされる芳香族化合物およびその
縮合環化合物とをモル比０．１：１〜１０：１で酸性触
媒下液相で反応させ一般式 ▲数式、化学式、表等があります▼・・・・・・・・・
・・・・・（３）で表わされる２，３−ジヒドロベンゾ
フランを生成させることを特徴とするクマラン類の製造
法。 （ここで、Ｒ＾１は炭素数２〜８のアルキル基、Ｒ＾２
は炭素数１〜６のアルキル基、Ｒ＾３は水素原子もしく
は芳香族環に任意の位置に置換されたアルキル基もしく
は縮合環、ｎは１〜３の整数値を示す）２）酸性触媒と
してパラトルエンスルフォン酸を使用する特許請求の範
囲第１項記載の製造法。 ３）酸性触媒として、パラトルエンスルフォン酸および
他の酸性触媒を使用する特許請求の範囲第１項記載の製
造法。[Claims] 1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
・・・・・・The aldehyde represented by (1) and the general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・・・・
...The aromatic compound represented by (2) and its condensed ring compound are reacted in a liquid phase under an acidic catalyst at a molar ratio of 0.1:1 to 10:1 to form the general formula ▲ mathematical formula, chemical formula, table, etc. There is▼・・・・・・・・・
... A method for producing coumarans, characterized by producing 2,3-dihydrobenzofuran represented by (3). (Here, R^1 is an alkyl group having 2 to 8 carbon atoms, R^2
is an alkyl group having 1 to 6 carbon atoms, R^3 is a hydrogen atom or an alkyl group substituted at any position on an aromatic ring, or a condensed ring, n is an integer value of 1 to 3) 2) As an acidic catalyst The manufacturing method according to claim 1, which uses para-toluenesulfonic acid. 3) The production method according to claim 1, wherein para-toluenesulfonic acid and other acidic catalysts are used as the acidic catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330188A JPH03190868A (en) | 1989-12-20 | 1989-12-20 | Production of coumaran |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330188A JPH03190868A (en) | 1989-12-20 | 1989-12-20 | Production of coumaran |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03190868A true JPH03190868A (en) | 1991-08-20 |
Family
ID=18229820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1330188A Pending JPH03190868A (en) | 1989-12-20 | 1989-12-20 | Production of coumaran |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03190868A (en) |
-
1989
- 1989-12-20 JP JP1330188A patent/JPH03190868A/en active Pending
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