JPS5822464B2 - Method for producing O-acylated products of cyclohexane-1,3-dione enols - Google Patents
Method for producing O-acylated products of cyclohexane-1,3-dione enolsInfo
- Publication number
- JPS5822464B2 JPS5822464B2 JP52092220A JP9222077A JPS5822464B2 JP S5822464 B2 JPS5822464 B2 JP S5822464B2 JP 52092220 A JP52092220 A JP 52092220A JP 9222077 A JP9222077 A JP 9222077A JP S5822464 B2 JPS5822464 B2 JP S5822464B2
- Authority
- JP
- Japan
- Prior art keywords
- picoline
- cyclohexane
- dione
- chloride
- mol
- 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
Links
- -1 cyclohexane-1,3-dione enols Chemical class 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical group CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 150000001266 acyl halides Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 2
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 241000238631 Hexapoda Species 0.000 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- HGMJETQBLLVMTR-UHFFFAOYSA-N methyl 4,4-dimethyl-2,6-dioxocyclohexane-1-carboxylate Chemical compound COC(=O)C1C(=O)CC(C)(C)CC1=O HGMJETQBLLVMTR-UHFFFAOYSA-N 0.000 claims 1
- 125000005270 trialkylamine group Chemical group 0.000 claims 1
- 239000013598 vector Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 12
- 159000000000 sodium salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical class O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- AOPBDTHQAIWWMI-UHFFFAOYSA-N 2,2-dimethylcyclohexane-1,3-dione Chemical compound CC1(C)C(=O)CCCC1=O AOPBDTHQAIWWMI-UHFFFAOYSA-N 0.000 description 1
- GZVPUQVQXOVAGT-UHFFFAOYSA-N 2,5-dimethylcyclohexane-1-carboxylic acid Chemical compound CC1CCC(C)C(C(O)=O)C1 GZVPUQVQXOVAGT-UHFFFAOYSA-N 0.000 description 1
- 241000551547 Dione <red algae> Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000006179 O-acylation Effects 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000006480 benzoylation reaction Methods 0.000 description 1
- 238000010514 butyrylation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- LPHLNZHFRMZONI-UHFFFAOYSA-N methyl(octyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[NH2+]C LPHLNZHFRMZONI-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は一般式
（式中、Ｒ１は低級アルキル基を、Ｒ２はアルキル基又
はフェニル基を示す。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein R1 represents a lower alkyl group and R2 represents an alkyl group or a phenyl group).
）で表わされるシクロヘキサン−１・３−ジオンエノー
ルの０−アシル化物の製造方法に関するものである。) The present invention relates to a method for producing an 0-acylated product of cyclohexane-1,3-dioneenol represented by:
前記一般式〔Ｉ〕または世で示される０−アシル化物を
転位して得られる２−アシル−シクロヘキサンート３−
ジオン類は次に示すように除草剤の中間体として極めて
有用な化合物である。2-acyl-cyclohexanate 3- obtained by rearranging the 0-acylated product represented by the general formula [I] or
Diones are extremely useful compounds as intermediates for herbicides, as shown below.
シクロヘキサン−１・３−ジオン類の０−アシ。0-acyl of cyclohexane-1,3-diones.
ル反応としては、シクロヘキサン−１・３−ジオン類と
過剰の酸無水物とを高温で反応させる方法（Ｂｅｒ、３
７．３３７０〜３３８５、Ａｎｎ、５７０．１〜１５（
１９５０）、Ｊ、 Ｃｈｅｒｎ、 Ｓｏｃ、８０３〜８
１０（１９５３））、２・５−ジメチルシクロヘキサン
ート３−ジオンエル−トのナトリウム塩をエーテル溶媒
中でメチルクロロホルメートと反応させる方法（Ｚｈｕ
ｒ、０ｂｓｈｃｈｅｉ Ｋｈｉｍ。A method for reacting cyclohexane-1,3-diones with excess acid anhydride at high temperature (Ber, 3
7.3370-3385, Ann, 570.1-15 (
1950), J. Chern, Soc, 803-8
10 (1953)), a method of reacting the sodium salt of 2,5-dimethylcyclohexanate 3-dione erth with methyl chloroformate in an ether solvent (Zhu
r, 0bshchei Khim.
３０．５４２〜５４５（１９６０）〕、５・５〜ジメチ
ルシクロヘキザン−１・３−ジオンと酸クロリドとを炭
酸カリウムの存在下に反応させる方法〔薬学雑誌７６．
１２５６〜１２５８ （１９５６）等が知られている。30.542-545 (1960)], 5.5-method of reacting dimethylcyclohexane-1,3-dione and acid chloride in the presence of potassium carbonate [Pharmaceutical Journal 76.
1256-1258 (1956) and the like are known.
これらの製造方法においては、原料として乾燥したシク
ロヘキサン−１・３−ジオン類又はそのナトリウム塩を
用いる必要があり、この場合に水を含んだ原料を使用す
れば収率の著しい低下等の好ましくない現象が起こる。In these production methods, it is necessary to use dried cyclohexane-1,3-diones or its sodium salt as a raw material, and in this case, if a raw material containing water is used, undesirable problems such as a significant decrease in yield may occur. A phenomenon occurs.
また、過剰の酸無水物又はエーテル溶媒の使用等工業的
、経済的に好ましい方法ではない。Further, the method is not industrially or economically preferable, such as using an excess of acid anhydride or ether solvent.
本発明方法の原料化合物である４−低級アルコキシ力ル
ボニル−５・５−ジメチルシクロヘキザ−１・３−ジオ
ン類（以下ＤＭＥという）又はそのナトリウム塩は、一
般に、マロン酸ニス７− ）Ｌ／ トメジチルオキシド
とナトリウムメチラートのメタノール溶液とを反応させ
て得られるが、目的とするＤＭＥ又はそのナトリウム塩
を収率よく且つ容易に分離するためには、上記反応液を
水中に注ぎ、メタノールを留去し、ナトリウム塩水溶液
として得る方法が採られる。4-Lower alkoxycarbonyl-5,5-dimethylcyclohexa-1,3-diones (hereinafter referred to as DME) or its sodium salt, which is a raw material compound in the method of the present invention, is generally used as a malonic acid varnish (7-) L/ It is obtained by reacting tomedityl oxide with a methanol solution of sodium methylate, but in order to easily separate the target DME or its sodium salt with good yield, the reaction solution is poured into water and the methanol is removed. A method of distilling it off to obtain an aqueous sodium salt solution is adopted.
従って原料の乾燥を必要とする従来の方法は工業的に好
ましくない。Therefore, conventional methods requiring drying of raw materials are industrially undesirable.
通常、酸塩化物等によるアシル化反応は無水の状態で行
われるものであるが、本発明者らはＤＭＥのＯ−アシル
化反応について種々研究した結果、γ−ピコリン等を触
媒として使用することにより、大量の水の存在下におい
てもＤＭＥの０−アシル化反応が殆んど定量的に進行す
ることを見い出し本発明を完成するに至った。Usually, the acylation reaction using acid chloride etc. is carried out in an anhydrous state, but as a result of various researches on the O-acylation reaction of DME, the present inventors found that it is possible to use γ-picoline etc. as a catalyst. As a result, the present inventors discovered that the 0-acylation reaction of DME proceeds almost quantitatively even in the presence of a large amount of water, leading to the completion of the present invention.
本発明は一般式
（式中、Ｒ１は前記の定義と同一）
で表わされる化合物のナトリウム塩等のアルカリ金属塩
水溶液と水に難溶な有機溶剤との混合物で、メチルピリ
ジン等の触媒の存在下において・・ロゲン化アシルを反
応させることからなるシクロヘキサンート３−ジオン類
のＯ−アシル化物の製造方法である。The present invention is a mixture of an aqueous solution of an alkali metal salt such as a sodium salt of a compound represented by the general formula (wherein R1 is the same as defined above) and an organic solvent that is sparingly soluble in water, in the presence of a catalyst such as methylpyridine. Below is a method for producing O-acylated products of cyclohexanate 3-diones, which comprises reacting acyl rogenoids.
尚、一般式叫で表わされる化合物は下記の互変異性体構
造をとり得る。Incidentally, the compound represented by the general formula can have the following tautomeric structure.
ＤＭＥのアルカリ金属塩としては、通常ナトリウム塩が
使用され、通常の方法で得られたＤＭＥを水酸化す（・
リウム水溶液と反応させることによｉつても容易に得ら
れる。As the alkali metal salt of DME, sodium salt is usually used, and DME obtained by a normal method is hydroxylated (
It can also be easily obtained by reacting with an aqueous solution of lithium.
この場合、原料ＤＭＥは含水物が使用できる。In this case, a hydrous material can be used as the raw material DME.
本発明で使用されるハロゲン化アシルとしては、飽和脂
肪酸クロリド、ベンゾイルクロリド等が挙げられる。Examples of the acyl halide used in the present invention include saturated fatty acid chloride, benzoyl chloride, and the like.
これらのアシル化剤はＤＭＥのアルカリ土類金属塩１モ
ル当り、工業的には通常１．０〜１．０５モルが使用さ
れる。These acylating agents are usually used industrially in an amount of 1.0 to 1.05 mol per mol of the alkaline earth metal salt of DME.
本発明で使用される触飽としては、ピリジンα−ピコリ
ン、β−ピコリン、γ−ピコリン等のピリジン類、トリ
エチルアミン、トｌルーｎ−ブチル１アミン、トリオク
チルアミン等の三級アミン類、トリオクチルメチルアン
モニウムクロリド、塩化ベンザルコニウムクロリド、ト
リーｎ−ブチルベンジルアンモニウムクロリド若しくは
プロミド等のハロゲン化四級アンモニウム類及びキノリ
ン等）が挙げられγ−ピコリンが工業的には最も好まし
い。The catalysts used in the present invention include pyridines such as pyridine α-picoline, β-picoline, and γ-picoline, tertiary amines such as triethylamine, tolu-n-butyl-1 amine, and trioctylamine, halogenated quaternary ammoniums such as octylmethylammonium chloride, benzalkonium chloride, tri-n-butylbenzylammonium chloride or bromide, and quinoline, and γ-picoline is industrially most preferred.
触媒の添加量は、その種類及びその他の反応条件により
異るが、ＤＭＥのアルカリ金属塩１モルに対し、０．０
０２モル以上であればよく、好ましくは０．００５〜０
．０３モルである。The amount of catalyst added varies depending on its type and other reaction conditions, but it is 0.0 per mol of DME alkali metal salt.
0.02 mole or more, preferably 0.005 to 0
．． 03 moles.
これらの触媒の使用は本発明の特徴の一つであり、これ
らの触媒は加水分解され易いハロゲン化アシルを選択的
にＤＭＥのアルカリ金属塩に反応させる働きをする。The use of these catalysts is one of the features of the present invention, and these catalysts serve to selectively react the easily hydrolyzed acyl halide with the alkali metal salt of DME.
反応系における水量は、一般にＤＭＥのアルカリ金属塩
水溶液の粘度が低く充分に攪拌できる量として、該原料
１モル当り２５０〜５００ｍ１が使用される。The amount of water in the reaction system is generally from 250 to 500 ml per mole of the raw material, as the aqueous solution of the alkali metal salt of DME has a low viscosity and can be sufficiently stirred.
使用する水難溶性有機溶剤としては、ジクロロメタン、
クロロホルム、ジクロロエタン、トリクレン、ハークレ
ン、ジクロロプロパン等のハロゲン化炭化水素溶剤、ベ
ンゼン、トルエン、キシレン等の芳香族炭化水素溶剤、
ヘキサン、リグロイン等の飽和脂肪族炭化水素溶剤が挙
げられる。The poorly water-soluble organic solvents used include dichloromethane,
Halogenated hydrocarbon solvents such as chloroform, dichloroethane, trichlene, haklene, dichloropropane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc.
Examples include saturated aliphatic hydrocarbon solvents such as hexane and ligroin.
有機溶剤の添加量は、その種類及び他の反応条件によっ
て異るが、ＤＭＥのアルカリ金属塩１モルに対して通常
２００〜１０００Ｔｔｌが使用される。The amount of organic solvent added varies depending on the type and other reaction conditions, but is usually 200 to 1000 Ttl per mol of the alkali metal salt of DME.
反応温度は反応系の条件によって異るが通常−５〜６０
°Ｃ１好ましくは０〜２０℃である。The reaction temperature varies depending on the conditions of the reaction system, but is usually -5 to 60℃.
°C1 is preferably 0 to 20 °C.
反応終了後は有機層を水層から分液して水洗濃縮等の処
理を行うことにより、ＤＭＥのＯ−アシル化物を取出す
ことができる。After the reaction is completed, the O-acylated DME can be extracted by separating the organic layer from the aqueous layer and performing treatments such as washing with water and concentration.
本発明の方法は、原料に乾燥したＤＭＥ又は１）ＭＥ−
Ｎａ塩を用いる必要がなく、また反応系に水を使うので
安全であり、また従来法に比し好収率である等工業的製
法としての利点を有するものであるが、更に次の様な効
果もある。The method of the present invention uses dried DME or 1) ME-
It is safe as it does not require the use of Na salts and water is used in the reaction system, and it has advantages as an industrial production method, such as a higher yield than conventional methods, but it also has the following advantages: It's also effective.
即ち、ＤＭＥのＯ−アシル化物を転位して２−アシル−
４−低級アルコキシカルボニル−５・５−ジメチルシク
ロヘキサン−１・３−ジオンを製造する場合、本発明方
法により得られるＤＭＥの０−アシル化物の溶液を脱水
することにより、そのま又転位反応を進行させることを
可能にする。That is, the O-acylated product of DME is rearranged to form 2-acyl-
When producing 4-lower alkoxycarbonyl-5,5-dimethylcyclohexane-1,3-dione, the rearrangement reaction can proceed directly by dehydrating the solution of the 0-acylated DME obtained by the method of the present invention. make it possible to
従って本発明は２−アシル−５・５−ジメチル−４−メ
トキシカルボニルシクロヘキサン−１・３−ジオンの製
造に対しても極めて有利な方法を提供するものである。Therefore, the present invention provides an extremely advantageous method for producing 2-acyl-5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dione.
本発明の方法はＤＭＥの０−アシル化反応のみならず、
類似化合物である他のシクロヘキサン−１・３−ジオン
類にも、触媒量、温度条件等を適宜選択することにより
適用可能である。The method of the present invention is not limited to the 0-acylation reaction of DME.
It can also be applied to other similar compounds, cyclohexane-1,3-diones, by appropriately selecting the amount of catalyst, temperature conditions, etc.
例えば、本発明の方法が適用可能な化合物をＤＭＥを含
めた一般式で表すと下記の通りである。For example, compounds to which the method of the present invention can be applied are represented by the following general formula including DME.
（式中、Ｘはアルキル基、低級アルコキシカルボニル基
、シアン基、フェニル基又は置換フェニル基を、ｎはＯ
ｌｌ、２又は３を示す。(In the formula, X is an alkyl group, lower alkoxycarbonyl group, cyan group, phenyl group or substituted phenyl group, n is O
Indicates ll, 2 or 3.
）） 以下に実施例を挙げて本発明を更に詳細に説明す
るが、本発明はこれらに限定されるものではない。)) The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto.
実施例 １
２１−フラスコにＤＭＥ（４−メトキシカルボ’ ＝ル
） １９８ Ｌ？（］ モ／Ｌ／）と水１４０ｙｕｌを
仕込み、冷却攪拌しながら２０％力性ソーダ水溶液２０
０グを１０分間にわたって滴下して、Ｄ Ｍ Ｅ −Ｎ
ａ塩水溶液を生成させた。Example 1 198 L of DME (4-methoxycarboxylic acid) was added to a 21-flask. (] Mo/L/) and 140 yul of water, and while cooling and stirring, 20% aqueous sodium chloride solution 20%
D M E -N by dropping 0 g over 10 minutes.
A salt aqueous solution was produced.
この中へＥＤＣ５００ＴＬｌγ−ピコリン０．４６５
′？（０，００５モル）を仕込み、）酪酸クロリド１０
６．５？（１，０モル）を１０〜２０℃で攪拌しながら
３０分にわたって滴下した。Into this EDC500TLlγ-picoline 0.465
′? (0,005 mol),)butyric acid chloride 10
6.5? (1.0 mol) was added dropwise over 30 minutes with stirring at 10-20°C.
滴下後、更に室温で３０分間反応した。After the dropwise addition, the mixture was further reacted at room temperature for 30 minutes.
反応後有機層を水層から分液し水洗した後、有機層を硫
酸マグネシウムで乾燥し、有機層を減圧濃縮すると淡黄
色油状物２６５．３？が得られた。After the reaction, the organic layer was separated from the aqueous layer and washed with water. The organic layer was dried over magnesium sulfate, and the organic layer was concentrated under reduced pressure. was gotten.
対ＤＭＥ収率９９．０％。Yield based on DME: 99.0%.
また、得られた淡黄色油状物を減圧蒸留することにより
５・５−ジメチル−４−メトキシカルボニルシクロヘキ
サン−１・３−ジオンエノールの０−ブチリル化物の無
色油状物２５４．６？を得た。Further, by distilling the obtained pale yellow oil under reduced pressure, a colorless oil of 0-butyrylation of 5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dioneenol was obtained (254.6? I got it.
沸点１４５°ｃ ／ １．８ ｍｍＨｇ 、収率９５，
０％。Boiling point 145°C / 1.8 mmHg, yield 95,
0%.
元素分析値はＣ＝６２．８３％、Ｈ＝７．４８％。Elemental analysis values are C=62.83% and H=7.48%.
（Ｃ１４Ｈ２Ｏ０５としての計算値Ｃ−６２゜６９％、
Ｈ＝７．４６％）であった。(Calculated value C-62°69% as C14H2O05,
H=7.46%).
実施例 ２
実施例１と同様にして、触媒はピリジン、β−ピコリン
、α−ピコリン、キノリン、トリエチルアミン、トリー
ｎ−ブチルアミン、トリーｎ−ブチルベンジルアンモニ
ウムクロリド又はプロミドを各々０．０３モル使用した
。Example 2 In the same manner as in Example 1, 0.03 mol of each of pyridine, β-picoline, α-picoline, quinoline, triethylamine, tri-n-butylamine, tri-n-butylbenzylammonium chloride or bromide was used as a catalyst.
又酪酸クロリドを０〜１０℃で滴下した。Furthermore, butyric acid chloride was added dropwise at 0 to 10°C.
反応後得られた５・５−ジメチル−４−メトキシカルボ
ニルシクロヘキサン＝１・３−ジオンエノールのＯ−ブ
チリル化物をガスクロマトグラフィーにより分析を行っ
た結果、それぞれの触媒を使用した場合の収率は９６〜
９９％であった。As a result of gas chromatography analysis of the O-butyrylated product of 5,5-dimethyl-4-methoxycarbonylcyclohexane=1,3-dioneenol obtained after the reaction, the yield when each catalyst was used was as follows. 96～
It was 99%.
実施例 ３
実施例１と同様にして、有機溶剤はトルエン又はキシレ
ンを各々５００ｍ１使用した。Example 3 In the same manner as in Example 1, toluene or xylene was used in an amount of 500 ml each as an organic solvent.
反応後得られた５・５−ジメチルシクロヘキサン−１・
３−ジオンエノールの０−ブチリル化物をガスクロマト
グラフィーにより分析を行なった結果、収率は９７〜９
８％であった。5,5-dimethylcyclohexane-1 obtained after the reaction
As a result of analyzing the 0-butyrylated product of 3-dione enol by gas chromatography, the yield was 97-9.
It was 8%.
実施例 ４
１００１反応容器にマロン酸ジメチル５．２８ ｋｇ（
４０モル）、メシチルオキシド３．９２に９（４０モル
）と２５％ナトリウムメチラート溶液から得られた、Ｄ
ＭＥ（４−メトキシカルボニル）〜Ｎａ塩８．５４ｋｇ
（３８，８−Ｅル）を含む水溶液２０．１８ｋｇとＥＤ
Ｃ１９４，ｅとγ−ピコリン１８．０４？（０，１９４
モル）とを仕込み、酪酸クロリド４．１７ｋｇ（３９，
１９モル）を２０〜３０℃で攪拌しながら３０分にわた
って滴下した。Example 4 5.28 kg of dimethyl malonate (
40 mol), obtained from a 25% sodium methylate solution with mesityl oxide 3.92 to 9 (40 mol), D
ME (4-methoxycarbonyl) ~ Na salt 8.54 kg
20.18 kg of an aqueous solution containing (38,8-El) and ED
C194,e and γ-picoline 18.04? (0,194
mol) and 4.17 kg (39, mol) of butyric acid chloride.
19 mol) was added dropwise over 30 minutes while stirring at 20-30°C.
滴下後、更に室温で３０分間反応した。After the dropwise addition, the mixture was further reacted at room temperature for 30 minutes.
反応後有機層を水層から分腋し、水洗した後、有機層を
共沸脱水した。After the reaction, the organic layer was separated from the aqueous layer, washed with water, and then azeotropically dehydrated.
共沸脱水後得られた５・５−ジメチル−４−メトキシカ
ルボニルシクロヘキサン−１・３−ジオンエノールの０
−ブチリル化物を含むＥＤＣ溶液２１．３７ｋｇをガス
クロマトグラフィーにより分析した結果、目的物１０．
２９ｋｇ（３８，４モル）を含有していた。0 of 5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dione enol obtained after azeotropic dehydration
- As a result of gas chromatography analysis of 21.37 kg of the EDC solution containing the butyrylated product, the target product 10.
It contained 29 kg (38.4 mol).
収率９９．０％。実施例 ５
実施例１と同様にして、ＤＭＥ１９８Ｐ（１モル）、力
性ソーダ４１’（１モル）γ−ピコリン０．９．１１’
（０，０１モル）、アセチルクロリド７８．５Ｐ（１モ
ル）から５・５−ジメチル−４−メトキシカルボニルシ
クロヘキサン−１・３−ジオンエノールのＯ−アセチル
化物の無色油状物２２３．１ ？（０，９３モル）を得
た。Yield 99.0%. Example 5 In the same manner as in Example 1, DME198P (1 mol), hydric soda 41' (1 mol), γ-picoline 0.9.11'
(0.01 mol), colorless oil of O-acetylated product of 5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dioneenol from acetyl chloride 78.5P (1 mol) 223.1 ? (0.93 mol) was obtained.
収率９３％。沸点１４７．５〜１４８℃／２．５ｍｍＨ
ｇ。Yield 93%. Boiling point 147.5-148℃/2.5mmH
g.
元素分析値はＣ＝５９．８９％ Ｈ＝６．７０％（Ｃ１
□Ｈ１６０５としての計算値Ｃ＝６０．００％Ｈ＝６．
６７％）であった。The elemental analysis values are C=59.89% H=6.70% (C1
□Calculated value as H1605 C=60.00%H=6.
67%).
実施例 ６
実施例１と同様にして、ＤＭＥ１９１’（１モル）、力
性ソーダ４０７（１モル）γ−ピコリン０．４７グ（０
，００５モル）、塩化ベンゾイル１．４０．５？（１モ
ル）から５・５−ジメチル−４−メトキシカルボニルシ
クロヘキサン−１・３−ジオンエノールのＯ−ベンゾイ
ル化物の黄色油状物２９．９′？（０，９９モル）を得
た。Example 6 In the same manner as in Example 1, DME 191' (1 mol), hydric soda 407 (1 mol), γ-picoline 0.47 g (0
,005 mol), benzoyl chloride 1.40.5? (1 mol) to O-benzoylation of 5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dioneenol as a yellow oil 29.9'? (0.99 mol) was obtained.
収率９９％。元素分析値はＣ＝６７．７６％、Ｈ＝５．
９０％、（Ｃ１□Ｈ１８０５としてＣ＝６７．５５％、
Ｈ−５，９６％、）であった。Yield 99%. Elemental analysis values are C=67.76%, H=5.
90%, (C=67.55% as C1□H1805,
H-5, 96%).
以下に触媒を加えない場合について、比較例を挙げる。Comparative examples in which no catalyst is added are given below.
比較例 １
触媒を添加せず実施例１と同様にして、ＤＭＥｌ、 ９
８ ？ （１モル）、力性ソーダ４０Ｐ（１モル）酪酸
クロリド１０６．５？（１モル）から得られたＥＤＣ溶
液をガスクロマトグラフィーにより分析した結果５・５
−ジメチル−４−メトキシ力ルポニルシクロヘキサンー
ト３−ジオンエノールの０−ブチリル化物を９１．１
？ （０，３４ｍｏｌ ）含有していた。Comparative Example 1 DMEl, 9 was prepared in the same manner as in Example 1 without adding a catalyst.
8? (1 mole), strength soda 40P (1 mole) butyric acid chloride 106.5? Results of analyzing the EDC solution obtained from (1 mol) by gas chromatography 5.5
-dimethyl-4-methoxyluponylcyclohexanate 3-dioneenol 0-butyrylated product at 91.1
? (0.34 mol).
Claims (1)
ルのアルカリ金属塩とハロゲン化アシルとを、ピリジン
類、トリアルギルアミン類、ハロゲン類、ハロゲン化四
級アンモニウム類及びキノリン類からなる群から選ばれ
た触媒の存在下に、水難溶性有機溶剤と水との混合物中
で反応させることを特徴とする 一般式 （式中、Ｒ２はアルキル基又はフェニル基を示す。 ）で表わされるシクロヘキサン−１・３−ジオンエノー
ル類のＯ−アシル化物の製造方法。 ２ 月虫媒がピリジン、γ−ピコリン、β−ピコリン、
α−ピコリン、トリアルキルアミン、塩化ベンザルコニ
ウム、ｌ□ ’） −ｎ−７”チルベンジルアンモニウ
ムクロリド若しくはプロミド又はキノリンである特許請
求の範囲第１項記載の製造方法。 ３ シクロヘキサン−１・３− ジオンエノールが４−
メトキシカルボニル−５・５−ジメチルシクロヘキサン
−１・３−ジオンエノールテアリ、ノ＼ロゲン化アシル
が酪酸クロリドである特許請求の範囲第１項記載の製造
方法。 ４ 触媒がγ−ピコリンである特許請求の範囲第３項記
載の製造方法。[Scope of Claims] 1. An alkali metal salt of cyclohexane-1,3-dioneenol represented by the general formula (wherein R1 represents a lower alkyl group) and an acyl halide are combined with pyridines, trialgylamine, etc. The reaction is carried out in a mixture of a poorly water-soluble organic solvent and water in the presence of a catalyst selected from the group consisting of , R2 represents an alkyl group or a phenyl group.) A method for producing an O-acylated cyclohexane-1,3-dione enol. 2 Moon insect vectors include pyridine, γ-picoline, β-picoline,
The manufacturing method according to claim 1, which is α-picoline, trialkylamine, benzalkonium chloride, l□′)-n-7” thylbenzylammonium chloride or bromide, or quinoline. 3 Cyclohexane-1.3 - Dioneenol is 4-
2. The manufacturing method according to claim 1, wherein the methoxycarbonyl-5,5-dimethylcyclohexane-1,3-dione enolteary and acyl chloride is butyric acid chloride. 4. The manufacturing method according to claim 3, wherein the catalyst is γ-picoline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52092220A JPS5822464B2 (en) | 1977-08-02 | 1977-08-02 | Method for producing O-acylated products of cyclohexane-1,3-dione enols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52092220A JPS5822464B2 (en) | 1977-08-02 | 1977-08-02 | Method for producing O-acylated products of cyclohexane-1,3-dione enols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5427547A JPS5427547A (en) | 1979-03-01 |
| JPS5822464B2 true JPS5822464B2 (en) | 1983-05-09 |
Family
ID=14048354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52092220A Expired JPS5822464B2 (en) | 1977-08-02 | 1977-08-02 | Method for producing O-acylated products of cyclohexane-1,3-dione enols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5822464B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040047880A (en) * | 2001-10-02 | 2004-06-05 | 닛뽕소다 가부시키가이샤 | Process for preparation of ethene derivatives |
-
1977
- 1977-08-02 JP JP52092220A patent/JPS5822464B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5427547A (en) | 1979-03-01 |
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