JPH03188044A - Production of acyloxyaliphatic hydrocarbon - Google Patents
Production of acyloxyaliphatic hydrocarbonInfo
- Publication number
- JPH03188044A JPH03188044A JP1328053A JP32805389A JPH03188044A JP H03188044 A JPH03188044 A JP H03188044A JP 1328053 A JP1328053 A JP 1328053A JP 32805389 A JP32805389 A JP 32805389A JP H03188044 A JPH03188044 A JP H03188044A
- Authority
- JP
- Japan
- Prior art keywords
- hydrocarbon
- alkali metal
- reaction
- formula
- general formula
- 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
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 16
- -1 alkali metal salt Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 abstract description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 4
- 229910052736 halogen Inorganic materials 0.000 abstract 3
- 125000005907 alkyl ester group Chemical group 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 125000004423 acyloxy group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- KPOHQIPNNIMWRL-UHFFFAOYSA-N 3-chloropropyl acetate Chemical compound CC(=O)OCCCCl KPOHQIPNNIMWRL-UHFFFAOYSA-N 0.000 description 5
- 150000008282 halocarbons Chemical class 0.000 description 5
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 3
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 3
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical compound ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 description 2
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- DSVGICPKBRQDDX-UHFFFAOYSA-N 1,3-diacetoxypropane Chemical compound CC(=O)OCCCOC(C)=O DSVGICPKBRQDDX-UHFFFAOYSA-N 0.000 description 1
- NIDSRGCVYOEDFW-UHFFFAOYSA-N 1-bromo-4-chlorobutane Chemical compound ClCCCCBr NIDSRGCVYOEDFW-UHFFFAOYSA-N 0.000 description 1
- PHHNNDKXQVKJEP-UHFFFAOYSA-N 1-bromo-5-chloropentane Chemical compound ClCCCCCBr PHHNNDKXQVKJEP-UHFFFAOYSA-N 0.000 description 1
- JTWWWQGSFTWWDL-UHFFFAOYSA-N 1-chloro-2-iodoethane Chemical compound ClCCI JTWWWQGSFTWWDL-UHFFFAOYSA-N 0.000 description 1
- SFOYQZYQTQDRIY-UHFFFAOYSA-N 1-chloro-3-iodopropane Chemical compound ClCCCI SFOYQZYQTQDRIY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction 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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医薬、農薬等の中間体、あるいは各種化学商
品の原料として有用なアシルオキシ脂肪族炭化水素の製
造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing acyloxyaliphatic hydrocarbons useful as intermediates for pharmaceuticals, agricultural chemicals, etc., or raw materials for various chemical products.
〔従来の技術および発明が解決しようとする課題〕従来
、アシルオキシ脂肪族炭化水素を製造する方法として、
次のような方法が用いられている。[Prior art and problems to be solved by the invention] Conventionally, as a method for producing acyloxyaliphatic hydrocarbons,
The following methods are used:
すなわち、相異なるハロゲン原子を有するジハロゲン化
炭化水素であるＩ−ブロモ−３−クロロプロパンと脂肪
族カルボン酸のアルカリ金属塩である酢酸カリウムを酢
酸溶媒中で反応させる方法である（Ｊｏｕｒｎａｌ ｏ
ｊ ｔｈｅ Ａｍｅｒｉｃｘｎ Ｃｈｅ＋ｎｉ（！ｌ
５ｏｃｉｅｔｙ ７０． ５６（１９５４０゜しかしな
がら、この方法は目的とする１−アセトキシ−３−クロ
ロプロパンの選択率が６８％しかなく、これ以外に１−
アセトレキ−３−ブロモプロパンおよび１．３−ジアセ
トキシプロパン等が副生じ、原料であるハロゲン化炭化
水素の一方のハロゲン原子のみを選択的にアシルオキシ
基に置換するには難しいものがあった。That is, it is a method in which I-bromo-3-chloropropane, which is a dihalogenated hydrocarbon having different halogen atoms, and potassium acetate, which is an alkali metal salt of an aliphatic carboxylic acid, are reacted in an acetic acid solvent (Journal o
j the Americanxn Che+ni(!l
5ociety 70. 56 (19540°) However, this method has a selectivity of only 68% for the target 1-acetoxy-3-chloropropane;
Acetleky-3-bromopropane, 1,3-diacetoxypropane, etc. are produced as by-products, and it is difficult to selectively substitute only one halogen atom of the halogenated hydrocarbon raw material with an acyloxy group.
又、特開昭６３−１５２３４１では、同反応を溶媒とし
てアルコール類、エーテル類および脂肪族ニトリル類等
、水溶性のものを用いて実施しており、好収率で目的物
が得られている。しかしながら、処理として大量の固体
をろ過しなければならず、工業的にはあまり好ましいも
のとは言い難い。Furthermore, in JP-A-63-152341, the same reaction was carried out using water-soluble solvents such as alcohols, ethers, and aliphatic nitriles, and the desired product was obtained in good yield. . However, as a treatment, a large amount of solid must be filtered, and this is not very desirable from an industrial perspective.
本発明者らは、上記の従来の欠点を解決すべく鋭意研究
を重ねた結果、相間移動触媒を用いることにより、相異
なるハロゲン原子を有するジハロゲン化炭化水素の一方
のハロゲン原子のみを選択的にアシルオキシ基に置換で
きることを見いだし、さらに水に難溶性の溶媒を反応溶
媒として用いることにより、後処理において水を加える
だけで生成した塩を極めて容易に分離できることを見い
出し本発明を完成するに至った。As a result of extensive research to solve the above-mentioned conventional drawbacks, the present inventors have found that by using a phase transfer catalyst, only one halogen atom of a dihalogenated hydrocarbon having different halogen atoms can be selectively transferred. They discovered that the acyloxy group can be substituted with an acyloxy group, and further discovered that by using a poorly water-soluble solvent as the reaction solvent, the resulting salt could be separated extremely easily by simply adding water in post-treatment, leading to the completion of the present invention. .
すなわち、本発明の要旨とすると所は、一般式（１）
％式％（１）
（ただし、ＸｌおよびＸ２は相異なるハロゲン原子であ
り、Ａはアルキレン基である）で示されるジハロゲン化
炭化水素と、一般式（ＩＴ）
ＲＣＯＯＭ （ＩＩ）（ただし、
Ｒはアルキル基であり、Ｍはアルカリ金属である。）
で示される脂肪族カルボン酸のアルカリ金属塩を、一般
式（ｍ）
Ｒ’４Ｎ＋Ｘ （ｍ）（ただし、
Ｒ′は炭化水素残基であり、Ｘはハロゲン原子である。That is, the gist of the present invention is that dihalogenated hydrocarbons represented by the general formula (1) % formula % (1) (wherein, Xl and X2 are different halogen atoms, and A is an alkylene group) and the general formula (IT) RCOOM (II) (however,
R is an alkyl group and M is an alkali metal. ) An alkali metal salt of an aliphatic carboxylic acid represented by the general formula (m) R'4N+X (m) (however,
R' is a hydrocarbon residue and X is a halogen atom.
）
で示される相間移動触媒の存在下、酢酸アルキルエステ
ル溶媒中で反応させることを特徴とする、一般式（ｍＶ
）
ＲＣＯＯ−Ａ−Ｘ３ （ｒＶ）
（ただし、Ｘ３はハロゲン原子であり、Ａはアルキレン
基であり、Ｒはアルキル基である。）で示されるアシル
オキシ脂肪族炭化水素の製造方法に関する。) in the presence of a phase transfer catalyst represented by the general formula (mV
) RCOO-A-X3 (rV) (wherein, X3 is a halogen atom, A is an alkylene group, and R is an alkyl group).
本発明によれば相異なる２種のハロゲン原子を有するジ
ハロゲン化水素の一方のハロゲン原子のみを選択的にア
シルオキシ基に置換することができる。しかも、反応溶
媒として水に難溶性の溶媒を用いるため、反応換水を加
えて生成した塩を溶解させることができる。According to the present invention, only one halogen atom of a dihydrogen halide having two different types of halogen atoms can be selectively substituted with an acyloxy group. Furthermore, since a solvent that is poorly soluble in water is used as the reaction solvent, the salt produced can be dissolved by adding reaction water.
その結果、従来法に比べて高い選択性、しかも高収率で
高品質の１−アセトキシ−３−クロロプロパン等を得る
ことができることから、工業的に極めて優れた方法と言
うことができる。As a result, it is possible to obtain high-quality 1-acetoxy-3-chloropropane and the like with higher selectivity and higher yield than conventional methods, so it can be said to be an extremely excellent method industrially.
本発明の一般式（Ｉ）で示される原料であるジハロゲン
化炭化水素において、ＸｌおよびＸ２で示されるハロゲ
ン原子は、フッ素、塩素、臭素、ヨウ素の各原子がある
がＸｌとＸ２のいずれか一方が塩素原子であり、他方が
臭素原子またはヨウ素原子である場合は、臭素原子また
はヨウ素原子がアシルオキシ基に高い選択率で置換され
、目的とするアシルオキシ脂肪族炭化水素の収率が大き
くなるため、本発明において好ましい態様である。In the dihalogenated hydrocarbon that is the raw material represented by the general formula (I) of the present invention, the halogen atoms represented by Xl and X2 include fluorine, chlorine, bromine, and iodine atoms, but either Xl or X2 When is a chlorine atom and the other is a bromine atom or an iodine atom, the bromine atom or iodine atom is substituted with the acyloxy group with high selectivity, and the yield of the target acyloxy aliphatic hydrocarbon increases. This is a preferred embodiment of the present invention.
又、一般式（Ｔ）中、Ａで示されるアルキレン基として
は、メチレン、エチレン、プロピレン、ブチレン、ペン
チレン、ヘキシレン等が挙げられる。Further, in the general formula (T), examples of the alkylene group represented by A include methylene, ethylene, propylene, butylene, pentylene, hexylene, and the like.
本発明において用いられる一般式（１）で表わされるジ
ハロゲン化炭化水素としては、ブロモクロロメタン、１
−ブロモ−２−クロロエタン、１−ブロモ−３−クロロ
プロパン、１−ブロモ−４−クロロブタン、１−ブロモ
−５−クロロペンタン、１−ブロモー６−ヘキサン、１
−ヨード−２−クロロエタン、１−ヨード−３−クロロ
プロパン、１−ヨード−２＝ブロモエタンが挙げられる
。The dihalogenated hydrocarbon represented by the general formula (1) used in the present invention includes bromochloromethane, 1
-Bromo-2-chloroethane, 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo-6-hexane, 1
-iodo-2-chloroethane, 1-iodo-3-chloropropane, and 1-iodo-2=bromoethane.
次に、もう一方の原料である一般式（ＩＩ）で表わされ
る脂肪族カルボン酸のアルカリ金属塩は、アルキル基の
炭素数が１〜６で、アルカリ金属としては、リチウム、
ナトリウム、カリウム、ルビジウムが挙げられるが、収
率の面でカリウムが好ましい。Next, the other raw material, an alkali metal salt of an aliphatic carboxylic acid represented by the general formula (II), has an alkyl group having 1 to 6 carbon atoms, and the alkali metal includes lithium,
Examples include sodium, potassium, and rubidium, with potassium being preferred in terms of yield.
本発明において用いられる一般式１）の相間移動触媒と
してはテトラメチルアンモニウムクロライド、ベンジル
トリメチルアンモニウムクロライド、ベンジルトリエチ
ルアンモニウムクロライド、ベンジルトリブチルアンモ
ニウムクロライド、テトラブチルアンモニウムクロライ
ド、テトラブチルアンモニウムブロマイド等が挙げられ
る。Examples of the phase transfer catalyst of general formula 1) used in the present invention include tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, and the like.
また、これらの使用量は一般式（Ｉ）で示されるハロゲ
ン化炭化水素１モルに対して０．００１〜０．００５モ
ルの範囲で使用するのが好ましい。Moreover, it is preferable that these are used in an amount of 0.001 to 0.005 mol per 1 mol of the halogenated hydrocarbon represented by the general formula (I).
溶媒としては、水に難溶のエステル類である酢酸アルキ
ルエステルが好ましい。たとえば、酢酸エチルエステル
、酢酸ｎ−ブチルエステル、酢酸イソブチルエステル、
等が挙げられる。As the solvent, acetic acid alkyl esters, which are esters that are sparingly soluble in water, are preferred. For example, ethyl acetate, n-butyl acetate, isobutyl acetate,
etc.
これらの溶媒の使用量は特に制限されないが、通常はハ
ロゲン化炭化水素に対して３〜１０倍モルの範囲で用い
ることが好ましい。The amount of these solvents to be used is not particularly limited, but it is usually preferable to use them in a molar range of 3 to 10 times the amount of the halogenated hydrocarbon.
本発明における反応は、反応温度が２０〜２００℃で、
好ましくは３０〜１００℃の範囲で進行する。The reaction in the present invention has a reaction temperature of 20 to 200°C,
Preferably, the process proceeds in the range of 30 to 100°C.
本発明の置換反応において一般式（１）で示されるハロ
ゲン化炭化水素と脂肪族カルボン酸のアルカリ金属塩は
理論量で反応させてもよいが、ハロゲン化炭化水素１モ
ルに対して脂肪族カルボン酸のアルカリ金属塩を１．０
−１．５モルの範囲で過剰に使用するのが好ましい。In the substitution reaction of the present invention, the halogenated hydrocarbon represented by the general formula (1) and the alkali metal salt of the aliphatic carboxylic acid may be reacted in stoichiometric amounts; 1.0 alkali metal salt of acid
It is preferable to use an excess in the range of -1.5 mol.
反応終了後、反応混合物に水を加えると生成した塩が溶
解できることから、ろ過等の手段をとることなく簡単な
分岐操作で後処理することができる。抽出液は減圧下蒸
留することにより目的物であるアシルオキシ脂肪族炭化
水素を容易に分離することができ同時に回収した溶媒は
そのまま再使用が可能である。After the reaction is completed, the salt produced can be dissolved by adding water to the reaction mixture, so it can be post-treated by a simple branching operation without using any means such as filtration. By distilling the extract under reduced pressure, the target acyloxyaliphatic hydrocarbon can be easily separated, and at the same time, the recovered solvent can be reused as is.
本発明を以下の実施例にて更に詳細に説明するが、これ
らに限定されるものではない。The present invention will be explained in more detail in the following examples, but is not limited thereto.
実施例１
還流冷却器、温度計及び攪拌機を取り付けた３００ ｍ
ｌの三つロフラスコに溶媒として酢酸イソブチル１３０
ｍｌを入れ、これに１−ブロム−３−クロルプロパン
（７８，７ｇ、 ０．５ｍｏｌ） 、酢酸カリウム（５
３，９ｇ、 ０．５５ａｏｌ） 、テトラブチルアンモ
ニウムブロマイド（０，５ｇ、 ０．００１６＋ａｏｌ
）を加えて５０℃で２０時間反応した。Example 1 300 m equipped with reflux condenser, thermometer and stirrer
Isobutyl acetate as a solvent in a three-necked flask with 130
1-bromo-3-chloropropane (78.7 g, 0.5 mol) and potassium acetate (5 mol).
3.9g, 0.55aol), tetrabutylammonium bromide (0.5g, 0.0016+aol)
) was added and reacted at 50°C for 20 hours.
反応液に水を２００ ｍｌを加えて振とう後、分液し有
機層を取り出し、さらに飽和食塩水１００ ｍｌを加え
て振とう後、分液して有機層を取り出した。After adding 200 ml of water to the reaction solution and shaking, the mixture was separated and the organic layer was taken out. 100 ml of saturated brine was added and shaken, then the layers were separated and the organic layer was taken out.
ころ、収率が９１％で生成していることを確認した。（
転化率９７．７％、選択率９３．６％）さらに、酢酸イ
ソブチルを回収後、減圧蒸留で１−アセトキシ−３−ク
ロロプロパン５８．０ｇを得た。沸点９７℃／７０ｍ＋
ｎＨｇ（蒸留収率８５％）実施例２
実施例１の反応温度を２５℃に換えて実施例１と同様の
操作で１−アセトキシ−３−クロロプロパンを得た。そ
の結果を表１に示した。It was confirmed that the product was produced at a yield of 91%. (
After recovering isobutyl acetate (conversion rate: 97.7%, selectivity: 93.6%), 58.0 g of 1-acetoxy-3-chloropropane was obtained by distillation under reduced pressure. Boiling point 97℃/70m+
nHg (distillation yield 85%) Example 2 1-acetoxy-3-chloropropane was obtained in the same manner as in Example 1 except that the reaction temperature in Example 1 was changed to 25°C. The results are shown in Table 1.
実施例３
実施例１のテトラブチルアンモニウムブロマイドの使用
量を換え、実施例１と同様の操作により１−アセトキシ
−３−クロロプロパンを得た。Example 3 1-acetoxy-3-chloropropane was obtained in the same manner as in Example 1 except that the amount of tetrabutylammonium bromide used was changed.
その結果を表１に示した。The results are shown in Table 1.
（反応スケールは実施例１と同様である。）ここでガス
クロマトグラフィーで定量したと〔発明の効果〕
本発明によれば、相異なる２種のハロゲン原子を有する
ハロゲン化炭化水素の一方のハロゲン原子のみを選択的
にアシルオキシ基に置換することができる。従って、特
定のハロゲン原子のみがアシルオキシ基に置換されたア
シルオキシ脂肪族炭化水素の選択性９０％以上と非常に
高く、収率も９１％と良好である。(The reaction scale is the same as in Example 1.) Here, as determined by gas chromatography, [Effects of the Invention] According to the present invention, one of the halogenated hydrocarbons having two different types of halogen atoms Only atoms can be selectively substituted with acyloxy groups. Therefore, the selectivity for acyloxyaliphatic hydrocarbons in which only specific halogen atoms are substituted with acyloxy groups is very high at 90% or more, and the yield is also as good as 91%.
また、反応後、水を加えて塩を溶解させるという手法に
より極めて容易に後処理をすることができる。Further, after the reaction, post-treatment can be carried out extremely easily by adding water to dissolve the salt.
従って、本発明は副反応による生成物が少なく、しかも
分離、精製が極めて容易に実施できることから、工業的
に極めて優れた方法と言うことが出来る。Therefore, the present invention can be said to be an extremely excellent method industrially because it produces fewer products due to side reactions and can be separated and purified very easily.
Claims (1)
り、Ａはアルキレン基である） で示されるジハロゲン化炭化水素と、 一般式（II） ＲＣＯＯＭ（II） （ただし、Ｒはアルキル基であり、Ｍはアルカリ金属で
ある。） で示される脂肪族カルボン酸のアルカリ金属塩を、 一般式（III） Ｒ′＿４Ｎ＾＋Ｘ＾−（III） （ただし、Ｒ′は炭化水素残基であり、Ｘはハロゲン原
子である。） で示される相間移動触媒の存在下、酢酸アルキルエステ
ル溶媒中で反応させることを特徴とする 一般式（IV） ＲＣＯＯ−Ａ−Ｘ３（IV） （ただし、Ｘ３はハロゲン原子であり、Ａはアルキレン
基であり、Ｒはアルキル基である。）で示されるアシル
オキシ脂肪族炭化水素の製造方法。[Claims] A dihalogenated hydrocarbon represented by the general formula (I) Formula (II) RCOOM (II) (However, R is an alkyl group, M is an alkali metal.) An alkali metal salt of an aliphatic carboxylic acid represented by the general formula (III) R'_4N^+X^ -(III) (However, R' is a hydrocarbon residue and X is a halogen atom.) A general formula characterized in that the reaction is carried out in an acetic acid alkyl ester solvent in the presence of a phase transfer catalyst represented by (IV) A method for producing an acyloxyaliphatic hydrocarbon represented by RCOO-A-X3(IV) (wherein, X3 is a halogen atom, A is an alkylene group, and R is an alkyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1328053A JPH03188044A (en) | 1989-12-18 | 1989-12-18 | Production of acyloxyaliphatic hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1328053A JPH03188044A (en) | 1989-12-18 | 1989-12-18 | Production of acyloxyaliphatic hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03188044A true JPH03188044A (en) | 1991-08-16 |
Family
ID=18205984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1328053A Pending JPH03188044A (en) | 1989-12-18 | 1989-12-18 | Production of acyloxyaliphatic hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03188044A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993008152A1 (en) * | 1991-10-18 | 1993-04-29 | Ihara Chemical Industry Co., Ltd. | Process for producing halomethyl ester of aliphatic carboxylic acid |
| WO1998014421A1 (en) * | 1996-10-02 | 1998-04-09 | Daiichi Pharmaceutical Co., Ltd. | Method for esterifying carboxylic compounds |
| JP2010531852A (en) * | 2007-07-02 | 2010-09-30 | シンケム | A new synthesis of fenofibrate |
| JP2016014003A (en) * | 2014-07-01 | 2016-01-28 | サミ ラブズ リミテッド | Synthesis of calebin-a and its biologically active analogs |
-
1989
- 1989-12-18 JP JP1328053A patent/JPH03188044A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993008152A1 (en) * | 1991-10-18 | 1993-04-29 | Ihara Chemical Industry Co., Ltd. | Process for producing halomethyl ester of aliphatic carboxylic acid |
| US5319132A (en) * | 1991-10-18 | 1994-06-07 | Ihara Chemical Industry Co., Ltd. | Process for producing halomethyl ester of aliphatic carboxylic acid |
| WO1998014421A1 (en) * | 1996-10-02 | 1998-04-09 | Daiichi Pharmaceutical Co., Ltd. | Method for esterifying carboxylic compounds |
| JP2010531852A (en) * | 2007-07-02 | 2010-09-30 | シンケム | A new synthesis of fenofibrate |
| JP2016014003A (en) * | 2014-07-01 | 2016-01-28 | サミ ラブズ リミテッド | Synthesis of calebin-a and its biologically active analogs |
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