JPS63152341A - Production of acyloxyhalogenated hydrocarbon - Google Patents
Production of acyloxyhalogenated hydrocarbonInfo
- Publication number
- JPS63152341A JPS63152341A JP20963886A JP20963886A JPS63152341A JP S63152341 A JPS63152341 A JP S63152341A JP 20963886 A JP20963886 A JP 20963886A JP 20963886 A JP20963886 A JP 20963886A JP S63152341 A JPS63152341 A JP S63152341A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- metal salt
- carboxylic acid
- aliphatic carboxylic
- hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- -1 alkali metal salt Chemical class 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 14
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 13
- 125000005843 halogen group Chemical group 0.000 claims abstract description 13
- 150000002170 ethers Chemical class 0.000 claims abstract description 7
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 5
- 229930195729 fatty acid Natural products 0.000 claims abstract description 5
- 239000000194 fatty acid Substances 0.000 claims abstract description 5
- 150000001298 alcohols Chemical class 0.000 claims abstract description 4
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000004423 acyloxy group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 4
- KPOHQIPNNIMWRL-UHFFFAOYSA-N 3-chloropropyl acetate Chemical compound CC(=O)OCCCCl KPOHQIPNNIMWRL-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical compound ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- SOHAVULMGIITDH-ZXPSTKSJSA-N (1S,9R,14E)-14-(1H-imidazol-5-ylmethylidene)-2,11-dimethoxy-9-(2-methylbut-3-en-2-yl)-2,13,16-triazatetracyclo[7.7.0.01,13.03,8]hexadeca-3,5,7,10-tetraene-12,15-dione Chemical compound C([C@]1(C2=CC=CC=C2N([C@@]21NC1=O)OC)C(C)(C)C=C)=C(OC)C(=O)N2\C1=C\C1=CNC=N1 SOHAVULMGIITDH-ZXPSTKSJSA-N 0.000 description 1
- DSVGICPKBRQDDX-UHFFFAOYSA-N 1,3-diacetoxypropane Chemical compound CC(=O)OCCCOC(C)=O DSVGICPKBRQDDX-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- HKQCJJOXYWQRFN-UHFFFAOYSA-N 1-bromo-2-iodoethane Chemical compound BrCCI HKQCJJOXYWQRFN-UHFFFAOYSA-N 0.000 description 1
- NIDSRGCVYOEDFW-UHFFFAOYSA-N 1-bromo-4-chlorobutane Chemical compound ClCCCCBr NIDSRGCVYOEDFW-UHFFFAOYSA-N 0.000 description 1
- JTYUIAOHIYZBPB-UHFFFAOYSA-N 1-bromo-6-chlorohexane Chemical compound ClCCCCCCBr JTYUIAOHIYZBPB-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
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- OQCDPFUVJUOTNX-UHFFFAOYSA-N 3-bromopropyl acetate Chemical compound CC(=O)OCCCBr OQCDPFUVJUOTNX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- SOHAVULMGIITDH-UHFFFAOYSA-N Oxaline Natural products O=C1NC23N(OC)C4=CC=CC=C4C3(C(C)(C)C=C)C=C(OC)C(=O)N2C1=CC1=CN=CN1 SOHAVULMGIITDH-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000003028 Stuttering Diseases 0.000 description 1
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000706 filtrate Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- AILKHAQXUAOOFU-UHFFFAOYSA-N hexanenitrile Chemical compound CCCCCC#N AILKHAQXUAOOFU-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 description 1
- YOSXTSJZQNTKKX-UHFFFAOYSA-M potassium;heptanoate Chemical compound [K+].CCCCCCC([O-])=O YOSXTSJZQNTKKX-UHFFFAOYSA-M 0.000 description 1
- BLGUIMKBRCQORR-UHFFFAOYSA-M potassium;hexanoate Chemical compound [K+].CCCCCC([O-])=O BLGUIMKBRCQORR-UHFFFAOYSA-M 0.000 description 1
- OPCDHYPGIGFJGH-UHFFFAOYSA-M potassium;pentanoate Chemical compound [K+].CCCCC([O-])=O OPCDHYPGIGFJGH-UHFFFAOYSA-M 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-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
- 159000000005 rubidium salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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、染料の中間体成因は各種化学薬
品の原料として有用なアシルオキシハロゲン化炭化水素
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 acyloxyhalogenated hydrocarbons, which are useful as intermediates for pharmaceuticals, agricultural chemicals, and dyes, and as raw materials for various chemicals.
従来、アシルオキシ・・ロゲン化炭化水素を製造する方
法として次のような方法が採用されてい念。即ち、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で
ある１−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とを酢酸溶媒中
で反応させる方法である〔ジャーナル・オン・ジ・アメ
リカン・ケミカル・ンサイエテイ（Ｊｏｕｒｎａｌ ｏ
ｆ ｔｈｅ ＡｍｅｒｉｃａｎＣｈｅｍｉｃａｌ ５ｏ
ｃｉｅｔｙ ）第７６巻５６〜５８頁１９５４年）。し
かしながら、この方法によると、下記の反応式
ＣＨ３ＣＯ０Ｋ
ＣＬ（ＣＨ２）５Ｂｒ ＣＬ（ＣＨ２）５
０ＣＯＣＨ５＋Ｂｒ（ＣＨ２）５０ＣＯＣＨ３＋ＣＨ３
ＣＯ０（ＣＨ２）５０ＣＯＣＨｓに示すとおり目的とす
る１−アセトキシ−３−クロロプロパンの選択率が６８
％でしかなく、これ以外に１−アセトキシ−３−ブロモ
プロパン及び１．３−ジアセトキシプロパンが多量副生
し、原料であるハロゲン化炭化水素の一方の−・ロゲン
原子のみを選択的にアシルオキシ基で置換させることは
困難であった。Conventionally, the following methods have been used to produce acyloxy-logenated hydrocarbons. That is, it is a method in which 1-bromo-3-chloropropane, which is a halogenated hydrocarbon having two different types of halogen atoms, and potassium acetate, which is an alkali metal salt of an aliphatic carboxylic acid, are reacted in an acetic acid solvent [Journal・On the American Chemical Society (Journal o
f the American Chemical 5o
76, pp. 56-58, 1954). However, according to this method, the following reaction formula CH3CO0K CL(CH2)5Br CL(CH2)5
0COCH5+Br(CH2)50COCH3+CH3
As shown in CO0(CH2)50COCHs, the selectivity of the target 1-acetoxy-3-chloropropane is 68
%, and in addition to this, a large amount of 1-acetoxy-3-bromopropane and 1,3-diacetoxypropane are produced as by-products, and only one of the -. It was difficult to substitute with groups.
本発明者らは、上記の従来方法の欠点に鑑み、相異なる
２種の−・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で置換
させる方法について鋭意研究を重ねてきた。その結果、
本発明者らは、上記の置換反応を特定の溶媒中で行なう
ことによって、・・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で置換させ得ること
を見い出し、本発明を完成させるに至った。In view of the drawbacks of the conventional methods described above, the present inventors have conducted extensive research on a method for selectively substituting only one halogen atom of a halogenated hydrocarbon having two different types of ---halogen atoms with an acyloxy group. I've been piling it up. the result,
The present inventors have discovered that by carrying out the above substitution reaction in a specific solvent, it is possible to selectively substitute only one halogen atom of a halogenated hydrocarbon with an acyloxy group, and have completed the present invention. I ended up letting it happen.
即ち、本発明は、一般式（Ｉ）
ＸＩ−Ａ−Ｘ２ （Ｉ）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
とをアルコール類。That is, the present invention combines a halogenated hydrocarbon represented by the general formula (I) XI-A-X2 (I) and an alkali metal salt of an aliphatic carboxylic acid into an alcohol.
エーテル類及び脂肪酸ニトリル類からなる群より選ばれ
た少くとも１種の溶媒中で反応させることを特徴とする
一般式（１）
％式％（
で示されるアシルオキシハロゲン化炭化水素の製造方法
である。A method for producing an acyloxyhalogenated hydrocarbon represented by the general formula (1), characterized in that the reaction is carried out in at least one solvent selected from the group consisting of ethers and fatty acid nitriles. .
本発明に於ける上記一般式（１）で示されるハロゲン化
炭化水素に於いて、Ｘｌ及びｘ２で示されるハロゲン原
子は、フッ素、塩素。In the halogenated hydrocarbon represented by the above general formula (1) in the present invention, the halogen atoms represented by Xl and x2 are fluorine and chlorine.
シュウ素、ヨウ素の各原子が何ら制限されずに用い得る
。これらのハロゲン原子の中でも、ｘｌとｘ２ の論ず
れか一方が塩素原子であり、他方がシュウ素原子又はヨ
ウ素原子である場合は、シュウ素原子又はヨウ素原子が
アシルオキシ基に高い選択率で置換され、目的とするア
シルオキシハロゲン化炭化水素の収率が大きくなるため
、本発明に於いて好まし論態様である。Each atom of oxaline and iodine can be used without any restriction. Among these halogen atoms, if one of xl and x2 is a chlorine atom and the other is a sulfur atom or an iodine atom, the sulfur atom or iodine atom is substituted with the acyloxy group with high selectivity. This is a preferred embodiment in the present invention because the yield of the target acyloxyhalogenated hydrocarbon is increased.
また、前記一般式（Ｉ）中、Ａで示されるアルキレン基
は、直鎖状及び分枝状のものが何ら制限なく使用し得る
が、直鎖状である方がアシルオキシ基による置換反応の
選択性が良好である。炭素数も特に制限されないが、一
般には１〜１２、特に１〜６であるものが好ましい。人
で示されるアルキレン基として、本発明で好適に採用さ
れるものを具体的に例示すると、メチレン基、エチレン
基、プロピレン基、ブチレン基、ペンチレン基、ヘキシ
レン基等を挙げることができる。In addition, in the general formula (I), the alkylene group represented by A may be linear or branched without any restriction, but a linear alkylene group is preferable for the substitution reaction with an acyloxy group. Good properties. Although the number of carbon atoms is not particularly limited, it is generally 1 to 12, particularly preferably 1 to 6. Specific examples of the alkylene group preferably employed in the present invention include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, and the like.
本発明に於いて、好適に用い得るハロゲン化炭化水素を
具体的に例示すると例えば次のとおりである。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、 １−７’ロモー５−１０ロベンタン、１−ブロモ
ー６−クロロヘキサン、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。In the present invention, specific examples of halogenated hydrocarbons that can be suitably used are as follows. Bromochloromethane, 1-bromo-2-chloroethane, 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-7'romo5-10 lobentane, 1-bromo6-chlorohexane, 1-iodo- 2-chloroethane, 1-iodo-3-chloropropane, 1-iodo-2-
Bromoethane.
１−ヨー１”−３−ブロモプロパン等ヲ挙ケルことがで
きる。Examples include 1-yo-1''-3-bromopropane.
次に、もう一方の原料である脂肪族カルボン酸のアルカ
リ金属塩としては、公知のものが何ら制限なく採用され
る。本発明に於いては、特に炭素数が１〜１２、さらに
１〜６の脂肪族カルボン酸のアルカリ金属塩を用いるこ
とが、得られるアシルオキシハロゲン化炭化水素の収率
が高（なるために好適である。Next, as the alkali metal salt of aliphatic carboxylic acid, which is the other raw material, any known salt can be used without any restriction. In the present invention, it is preferable to use an alkali metal salt of an aliphatic carboxylic acid having 1 to 12 carbon atoms, particularly 1 to 6 carbon atoms, because the yield of the obtained acyloxyhalogenated hydrocarbon is high. It is.
また、アルカリ金属塩としては、リチウム塩。Also, as an alkali metal salt, lithium salt is used.
ナトリウム塩、カリウム塩、ルビジウム塩等特に制限さ
れたーが、カリウム塩を用いることが上記と同様の理由
により好適である。Although sodium salts, potassium salts, rubidium salts, etc. are particularly limited, it is preferable to use potassium salts for the same reason as above.
本発明に於いて、好適に用い得る脂肪族カルボン酸のア
ルカリ金属塩を例示すると、酢酸カリウム、プロピオン
酸カリウム、酪酸カリウム、吉草酸カリウム、カプロン
酸カリウム、エナント酸カリウム、アクリル酸カリウム
、メタクリル酸カリウム等を挙げることができる。In the present invention, examples of alkali metal salts of aliphatic carboxylic acids that can be preferably used include potassium acetate, potassium propionate, potassium butyrate, potassium valerate, potassium caproate, potassium enanthate, potassium acrylate, and methacrylic acid. Potassium etc. can be mentioned.
本発明に於いては、前記したー・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との反応をアルコール
類、エーテル類及び脂肪酸ニトリル類よりなる群から選
ばれた少くとも１種以上の溶媒中で行なうことが最大の
特徴である。In the present invention, the above-described reaction between the halogenated hydrocarbon and the alkali metal salt of an aliphatic carboxylic acid is carried out using at least one kind selected from the group consisting of alcohols, ethers and fatty acid nitriles. The biggest feature is that it is carried out in a solvent.
アルコール類としては、公知のものが伺ら制限なく使用
し得る。特に炭素数２〜５の１級又は２級の低級アルコ
ールが好ましい。例えば、エタノール、ｎ−プロパツー
ル、インプロパツール、ｎ−ブタノール、イソブタノー
ル、ｎ−アξルアルコール、インアミルアルコール等を
挙げることができる。また、エーテル類としては、炭素
数２〜５の低級エーテルが好ましい。例えば、ジメチル
エーテル。As the alcohol, any known alcohol may be used without any restriction. In particular, primary or secondary lower alcohols having 2 to 5 carbon atoms are preferred. Examples include ethanol, n-propertool, inpropertool, n-butanol, isobutanol, n-alcohol, in-amyl alcohol, and the like. Furthermore, as the ethers, lower ethers having 2 to 5 carbon atoms are preferred. For example, dimethyl ether.
ジエチルエーテル、メチルエチルエーテル。Diethyl ether, methyl ethyl ether.
メチルプロピルエーテル等の鎖状エーテル；ジオキサン
、テトラヒドロフラン等の環状エーテル等を挙げること
ができる。Examples include chain ethers such as methylpropyl ether; cyclic ethers such as dioxane and tetrahydrofuran.
また、脂肪酸二） ＩＪシル類しては、特に制限されず
公知のものが使用し得るが、炭素数が１〜５であること
が好ましｂｏ例えば、アセトニ） ＩＪル、シアン化エ
チル、シアン化ｎ−プロピル、シアン化ｎ−ブチル、シ
アン化ｎ−ペンチル等が本発明に於いて好適に使用し得
る。In addition, the fatty acid (2) IJ is not particularly limited and any known one can be used, but it is preferable that the number of carbon atoms is 1 to 5. For example, acetonyl, ethyl cyanide, cyanide, etc. N-propyl cyanide, n-butyl cyanide, n-pentyl cyanide, etc. can be suitably used in the present invention.
これらの溶媒の使用量は、特に制限されず、通常の有機
合成反応における溶媒量で良ｈ０本発明にお込ては、通
常はハロゲン化炭化水素に対して３〜１０倍モルの範囲
で溶媒を用することが好ましい。The amount of these solvents to be used is not particularly limited, and in the present invention, the amount of solvent used in ordinary organic synthesis reactions is sufficient. It is preferable to use
本発明における反応は所定の溶媒に、一般式（１）で示
される一ロゲン化炭化水素を溶解し、脂肪族カルボン酸
のアルカリ金属塩を添加して加熱攪拌することにより行
なわれる。The reaction in the present invention is carried out by dissolving the monologenated hydrocarbon represented by the general formula (1) in a predetermined solvent, adding an alkali metal salt of an aliphatic carboxylic acid, and stirring with heating.
本発明による置換反応は反応温度２０〜２００℃、好ま
しくは３０〜１５０℃の範囲で好適に進行する。溶媒の
沸点の関係で、耐圧容器中加圧下で行なうことも可能で
ある。The substitution reaction according to the present invention proceeds suitably at a reaction temperature of 20 to 200°C, preferably 30 to 150°C. Depending on the boiling point of the solvent, it is also possible to conduct the reaction under pressure in a pressure-resistant container.
本発明による置換反応において、一般式（Ｉ）で示され
るー・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吃よいが、ハロゲン化炭化
水素１モルに対し脂肪族カルボン酸のアルカリ金属塩を
１．０〜２．０モルの範囲で、特に１．０〜１．５モル
の範囲で過剰に使用するのが好ましい。また、反応を促
進するため各種相関移動触媒も適宜用いることができる
。反応終了後、生成した塩は濾過等の手段により除いた
あと一反応溶液を減圧下蒸留することにより目的物であ
る一般式（１）で示されるアシルオキシ−・ロゲン化炭
化水素を容易に分離することが出来る。In the substitution reaction according to the present invention, the halogenated hydrocarbon represented by the general formula (I) and the alkali metal salt of an aliphatic carboxylic acid are reacted in stoichiometric amounts to produce a stuttering reaction. It is preferred to use the alkali metal salt of group carboxylic acid in excess in the range of 1.0 to 2.0 mol, particularly in the range of 1.0 to 1.5 mol. Moreover, various phase transfer catalysts can also be used as appropriate to promote the reaction. After the reaction is completed, the produced salt is removed by means such as filtration, and the reaction solution is distilled under reduced pressure to easily separate the target acyloxy-logenated hydrocarbon represented by general formula (1). I can do it.
同時に回収した溶媒はそのまま再使用が可能である。The solvent recovered at the same time can be reused as is.
以上の方法により、一般式（ｆ［）で示されるアシルオ
キシハロゲン化炭化水素を選択性良く得ることができる
。前記一般式（１）中、Ｒは脂肪族炭化水素残基であり
、これは、原料として用いる脂肪族カルボン酸のアルカ
リ金属塩の種類に対応するものである。また、前記一般
式（Ｉｆ）中、 ｘ５及びＡは前記一般式（Ｉ）で述
べた刈及びＡと同様である。By the above method, the acyloxyhalogenated hydrocarbon represented by the general formula (f[) can be obtained with good selectivity. In the general formula (1), R is an aliphatic hydrocarbon residue, which corresponds to the type of alkali metal salt of aliphatic carboxylic acid used as a raw material. Furthermore, in the general formula (If), x5 and A are the same as Kari and A described in the general formula (I).
本発明の方法によれば、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
れたアシルオキシハロゲン化炭化水素が極めて選択性良
く、例えば、７５％以上の選択率で得ることができる。According to the method of the present invention, only one halogen atom of a halogenated hydrocarbon having two different types of halogen atoms can be selectively substituted with an acyloxy group. Therefore, acyloxyhalogenated hydrocarbons in which only specific halogen atoms are substituted with acyloxy groups can be obtained with extremely high selectivity, for example, with a selectivity of 75% or more.
特に、脂肪族カルボン醗のカリウム塩を原料として用い
た場合には、目的物の収率も７０％以上と良好である。In particular, when a potassium salt of aliphatic carboxyl alcohol is used as a raw material, the yield of the target product is as good as 70% or more.
従って、副反応による生成物が少な込ために、目的とす
るアシルオキシハロゲン化炭化水素の分離及び精製も極
めて容易に行なうことができる。Therefore, since there are fewer products resulting from side reactions, the target acyloxyhalogenated hydrocarbon can be separated and purified very easily.
実施例 １
還流冷却器、温度計および攪拌機を取りつけた３００−
の三つロフラスコに溶媒としてアセトニトリル１５１ｓ
ｄ（２，５モル）を入れ、これ′Ｖｃ１−プロモー３−
クロロプロパン７Ｂ、７１（０，５モル）、酢酸カリウ
ム５３．９．９ （０，５５モル）を加えて、アセトニ
トリル還流下１２時間反応した。反応液を室温まで冷却
後、生成した固体を濾過により除去し、固体はアセトニ
トリル５３ｍ１（１モル）で洗浄した。濾液と洗液とを
あわせ、ガスクロマトグラフィーで定量して１−アセト
キシ−３−クロロプロパンが収車９１％で生成している
ことを確認した。（転化率９６．３％９選択率９４．５
％）。Example 1 300- equipped with reflux condenser, thermometer and stirrer
Acetonitrile 151s as a solvent in a three-necked flask.
d (2.5 mol) and this 'Vc1-promo 3-
Chloropropane 7B, 71 (0.5 mol) and potassium acetate 53.9.9 (0.55 mol) were added and reacted for 12 hours under refluxing acetonitrile. After cooling the reaction solution to room temperature, the generated solid was removed by filtration, and the solid was washed with 53 ml (1 mol) of acetonitrile. The filtrate and washing liquid were combined and quantitatively determined by gas chromatography to confirm that 1-acetoxy-3-chloropropane was produced in 91% of the collected vehicles. (Conversion rate 96.3% 9 Selectivity 94.5
%).
さらに減圧蒸留して１−アセトキシ−６−クロロプロパ
ン５４Ｉ！を得た。沸点７４〜７６’Ｃ／ ２２ ｖｓ
Ｈｇ （収率８０％）。Further distillation under reduced pressure yields 1-acetoxy-6-chloropropane 54I! I got it. Boiling point 74-76'C/22 vs.
Hg (80% yield).
実施例 ２
実施例１で用いた溶媒のアセトニトリルを表１に示した
溶媒に換え、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。Example 2 1-acetoxy-
3-chloropropane was obtained. The results are shown in Table 1.
実施例 ３
実施例１と同様にして表２に示したノ〜ロゲン化炭化水
素、脂肪族カルボン酸のアルカリ金属塩及び溶媒を用い
て反応を行なった。その結果を表２に示した。Example 3 A reaction was carried out in the same manner as in Example 1 using the halogenated hydrocarbons, alkali metal salts of aliphatic carboxylic acids, and solvents shown in Table 2. The results are shown in Table 2.
Claims (1)
り、Ａはアルキレン基である。〕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とをアル
コール類、エーテル類及び脂肪酸ニトリル類からなる群
より選ばれた少くとも１種の溶媒中で反応させることを
特徴とする一般式 ＲＣＯＯ−Ａ−Ｘ＿３ 〔但し、Ｘ＿３はハロゲン原子であり、Ａ はアルキレン基であり、Ｒは脂肪族炭化 水素残基である。〕 で示されるアミルオキシハロゲン化炭化水素の製造方法
。[Claims] General formula X_1-A-X_2 [However, X_1 and X_2 are different halogen atoms, and A is an alkylene group. ] is characterized by reacting the halogenated hydrocarbon represented by the formula with an alkali metal salt of an aliphatic carboxylic acid in at least one solvent selected from the group consisting of alcohols, ethers, and fatty acid nitriles. General formula RCOO-A-X_3 [However, X_3 is a halogen atom, A is an alkylene group, and R is an aliphatic hydrocarbon residue. ] A method for producing an amyloxyhalogenated hydrocarbon represented by
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19393786 | 1986-08-21 | ||
| JP61-193937 | 1986-08-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63152341A true JPS63152341A (en) | 1988-06-24 |
| JPH0639450B2 JPH0639450B2 (en) | 1994-05-25 |
Family
ID=16316224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61209638A Expired - Lifetime JPH0639450B2 (en) | 1986-08-21 | 1986-09-08 | Method for producing acyloxyhalogenated hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0639450B2 (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 |
| US5774550A (en) * | 1994-04-01 | 1998-06-30 | Mercedes-Benz Ag | Vehicle security device with electronic use authorization coding |
| WO1999059947A1 (en) * | 1998-05-15 | 1999-11-25 | Commonwealth Industrial Research Organisation | Process for preparing ethers and esters |
| JP2002121175A (en) * | 2000-10-13 | 2002-04-23 | F-Tech Inc | Method for recovering aprotic polar solvent in producing trifluoroethylcarboxylic ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5225711A (en) * | 1975-08-23 | 1977-02-25 | Kaken Pharmaceut Co Ltd | Process for preparation of novel long chain unsaturated alcoholesters |
| JPS57139040A (en) * | 1981-02-21 | 1982-08-27 | Yodogawa Seiyaku Kk | Preparation of di-n-propymalonic acid ester |
-
1986
- 1986-09-08 JP JP61209638A patent/JPH0639450B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5225711A (en) * | 1975-08-23 | 1977-02-25 | Kaken Pharmaceut Co Ltd | Process for preparation of novel long chain unsaturated alcoholesters |
| JPS57139040A (en) * | 1981-02-21 | 1982-08-27 | Yodogawa Seiyaku Kk | Preparation of di-n-propymalonic acid ester |
Cited By (6)
| 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 |
| US5774550A (en) * | 1994-04-01 | 1998-06-30 | Mercedes-Benz Ag | Vehicle security device with electronic use authorization coding |
| WO1999059947A1 (en) * | 1998-05-15 | 1999-11-25 | Commonwealth Industrial Research Organisation | Process for preparing ethers and esters |
| JP2002121175A (en) * | 2000-10-13 | 2002-04-23 | F-Tech Inc | Method for recovering aprotic polar solvent in producing trifluoroethylcarboxylic ester |
| JP4698812B2 (en) * | 2000-10-13 | 2011-06-08 | 東ソ−・エフテック株式会社 | Method for recovering aprotic polar solvent in the production of trifluoroethyl (meth) acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0639450B2 (en) | 1994-05-25 |
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