JPS63287739A - Production of chloroacetals - Google Patents
Production of chloroacetalsInfo
- Publication number
- JPS63287739A JPS63287739A JP12225487A JP12225487A JPS63287739A JP S63287739 A JPS63287739 A JP S63287739A JP 12225487 A JP12225487 A JP 12225487A JP 12225487 A JP12225487 A JP 12225487A JP S63287739 A JPS63287739 A JP S63287739A
- Authority
- JP
- Japan
- Prior art keywords
- alcohol
- raw material
- tert
- chloroethyl
- amine
- 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
- 238000004519 manufacturing process Methods 0.000 title description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 30
- -1 Amine hydrochloride Chemical class 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- 150000001412 amines Chemical class 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 42
- 239000010410 layer Substances 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- OVXJWSYBABKZMD-UHFFFAOYSA-N 2-chloro-1,1-diethoxyethane Chemical compound CCOC(CCl)OCC OVXJWSYBABKZMD-UHFFFAOYSA-N 0.000 description 5
- CRZJPEIBPQWDGJ-UHFFFAOYSA-N 2-chloro-1,1-dimethoxyethane Chemical compound COC(CCl)OC CRZJPEIBPQWDGJ-UHFFFAOYSA-N 0.000 description 5
- QSKPIOLLBIHNAC-UHFFFAOYSA-N 2-chloro-acetaldehyde Chemical compound ClCC=O QSKPIOLLBIHNAC-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CDHLQZJRWKQATP-UHFFFAOYSA-N 1,1-dichloro-2,2-diethoxyethane Chemical compound CCOC(C(Cl)Cl)OCC CDHLQZJRWKQATP-UHFFFAOYSA-N 0.000 description 2
- XKRBMZSZPSBGLI-UHFFFAOYSA-N 2-chloro-1-ethoxy-1-methoxyethane Chemical compound CCOC(CCl)OC XKRBMZSZPSBGLI-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NGVTXINFTCZHGA-UHFFFAOYSA-N 1,1-dichloro-2,2-dimethoxyethane Chemical compound COC(OC)C(Cl)Cl NGVTXINFTCZHGA-UHFFFAOYSA-N 0.000 description 1
- GESXYYPKJBMNON-UHFFFAOYSA-N 1,1-dichloro-2-ethoxyethane Chemical compound CCOCC(Cl)Cl GESXYYPKJBMNON-UHFFFAOYSA-N 0.000 description 1
- GPTVQTPMFOLLOA-UHFFFAOYSA-N 1-chloro-2-ethoxyethane Chemical compound CCOCCCl GPTVQTPMFOLLOA-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000000638 solvent extraction 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）
本発明は医薬及び農薬の中間原料として有用なりロルア
セタール類の製造法に関する。例えばクロルアセトアル
デヒドジメチルアセタールである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing loracetals, which are useful as intermediate raw materials for pharmaceuticals and agricultural chemicals. For example, chloracetaldehyde dimethyl acetal.
（従来技術）
クロルアセクール類の製法としては（Ｉ）クロルアセト
アルデヒドとアルコールよシ無水塩化カルシウム等で脱
水反応した後有機層を精留する方法（Ｆ艮１，４９１，
４０６． ■１，２ ａ ５，８ ｓ ｏ ）。(Prior art) The method for producing chloracecools is (I) a method of dehydrating chloracetaldehyde with alcohol, anhydrous calcium chloride, etc., and then rectifying the organic layer (F 1,491,
406. ■1,2 a 5,8 s o ).
（ｎ） アルコール溶媒中へ酢酸ビニルと塩素ガスを
同時に仕込みながら一１０〜２０℃で反応し。(n) React at -10 to 20°C while simultaneously charging vinyl acetate and chlorine gas into an alcohol solvent.
室温にて一夜熟成した抜水を加えて有機層を分液する。The organic layer is separated by adding drained water that has been aged overnight at room temperature.
更に水層よりクロルアセタール類を抽出し、有機層と抽
出液を合わせて精留する方法（ＧＢ２．１４６，０１６
）。Furthermore, chloroacetals are extracted from the aqueous layer, and the organic layer and the extract are combined and rectified (GB2.146,016
).
０ ベンゼン溶媒中酢酸ヒニルを一１〜４℃で塩素化後
、アルコールを加えて一夜熟成を取り。0 After chlorinating hinyl acetate in a benzene solvent at -1 to 4°C, alcohol was added and aged overnight.
ベンゼン層を分液後共沸脱水にて反応を完結する。After separating the benzene layer, the reaction is completed by azeotropic dehydration.
この均一層を２０％苛性ソーダー水溶液にて中和後ベン
ゼン層と水層に分液し、水層よりクロルアセタールをベ
ンゼン抽出し、これを最初のペンゼン層と自わせて精留
する方法（ＵＳＰ ４，５３２，３３８）等が公知であ
る。This homogeneous layer is neutralized with a 20% caustic soda aqueous solution, separated into a benzene layer and an aqueous layer, and the chloroacetal is extracted from the aqueous layer with benzene. 4,532,338) and the like are publicly known.
（発明が解決しようとする問題点）
従来技術（１）は原料クロルアセトアルデヒドの市販品
は４０〜４５％と低濃度であり、クロルアセクール原料
としては８０％以上のクロルアセトアルデヒドを必要と
するが、高濃度クロルアセトアルデヒドは不安定で貯蔵
が困難なため、クロルアセトアルデヒドとクロルアセタ
ールを平行して製造しなければならない。そのためには
２系列の反応及び精製設備が必要になり工業的に不利で
ある。(Problems to be Solved by the Invention) Prior art (1) is that the commercially available raw material chloracetaldehyde has a low concentration of 40 to 45%, and 80% or more of chloracetaldehyde is required as a raw material for chloracecool. , Since high concentration chloracetaldehyde is unstable and difficult to store, chloracetaldehyde and chloracetal must be produced in parallel. This requires two lines of reaction and purification equipment, which is industrially disadvantageous.
又、従来技術（ＩＩ）及び（２）は塩素化に引続いて１
６時間以上も熟成を必要とし、製造能力が低い上に多量
の酢酸を副生ずるために、精製及び副生酢酸の回収に複
数の設備が必要になり工業的製法としては不利である。Furthermore, in the prior art techniques (II) and (2), following chlorination, 1
It requires aging for more than 6 hours, has low production capacity, and produces a large amount of acetic acid as a by-product, so multiple facilities are required for purification and recovery of the by-product acetic acid, which is disadvantageous as an industrial production method.
本発明は工業的により簡単な方法で安価に高品質のクロ
ルアセタール類を提供せんとするものである。The present invention aims to provide high quality chloroacetals at low cost using an industrially simpler method.
（問題点′ｌｆ：解決するための手段）本発明者はかか
る問題を解決するために鋭意検討した結果α、β−クロ
ルエチルアルキルエーテルとアルコールを混合するだけ
でクロルアセクール類を生成し、この混合物より脱塩酸
することによシはぼ定量的にクロルアセクール類が得ら
れることを見い出し本発明に致った。(Problem 'lf: Means for Solving) As a result of intensive studies to solve this problem, the inventors of the present invention have found that chloracecures are produced simply by mixing α,β-chloroethyl alkyl ether and alcohol. It was discovered that by dehydrochlorinating this mixture, chloracecoles could be obtained almost quantitatively, leading to the present invention.
即ち１本発明は脱塩酸剤の存在下、α、β−クロルエチ
ルアルキルニーテルトＣ４〜Ｃ４ノアルコー人２
Ｘ、およびＸ２は水素又は塩素を、Ｒ及びＲ１はｃ１〜
Ｃ４ノアルキル基を示す）で表わされるクロルアセクー
ル類の新規な製造法である。Namely, 1. In the presence of a dehydrochlorination agent, α,β-chloroethylalkylnitrate C4-C4 alcoholic acid 2X and X2 are hydrogen or chlorine, R and R1 are c1-
This is a novel method for producing chloracecules represented by C4 noalkyl group.
本発明に使用されるα、β−クロルエチルアルキリ）の
製造法としては（Ｉ） ハラアセトアルデヒドとアルコ
ールの混合物に常温で塩素ガスを導入することによりα
、β−クロルエチルアルキルエーテル層と塩酸水の混合
物として得られ、塩酸水を分離することにより純度８０
〜９０％のα、β−クロルエチルアルキルエーテルとし
て得る方法（特公昭２４−４３３１）。The method for producing α,β-chloroethylalkyl used in the present invention is (I) by introducing chlorine gas into a mixture of halacetaldehyde and alcohol at room temperature.
, obtained as a mixture of β-chloroethyl alkyl ether layer and hydrochloric acid water, and by separating the hydrochloric acid water, purity of 80
A method for obtaining ~90% α,β-chloroethyl alkyl ether (Japanese Patent Publication No. 4331/1989).
（［１） ノｅラアセトアルデヒドとアルコールの混
合物に常温で塩化水素ガスを導入することによりα−ク
ロルエチルアルキルエーテル（有機層）と塩酸水の混合
物が得られ、この有機層を分離し更に常温で塩素ガスを
導入することにより、純度９０〜９５％のα、β−クロ
ルエチルアルキルエーテルとして得る方法（特公昭２６
−２８２）等が公知である。([1) By introducing hydrogen chloride gas into a mixture of acetaldehyde and alcohol at room temperature, a mixture of α-chloroethyl alkyl ether (organic layer) and hydrochloric acid water is obtained, and this organic layer is separated and further heated at room temperature. A method of obtaining α,β-chloroethyl alkyl ether with a purity of 90 to 95% by introducing chlorine gas into
-282) etc. are publicly known.
前述の公知技術で得られるα、β−クロルエチルアルキ
ルエーテルは１０〜２０段の精留塔で減圧蒸留すること
により純度９７〜９８％まで純度を向上することができ
るが、蒸留中にα、β−クロルエチルアルキルエーテル
が分解し低収率になるため工業的製法としては不利であ
る。The purity of α,β-chloroethyl alkyl ether obtained by the above-mentioned known technique can be improved to 97-98% by distilling it under reduced pressure in a rectification column with 10 to 20 stages. This is disadvantageous as an industrial production method because the β-chloroethyl alkyl ether decomposes and the yield is low.
しかし本発明においては、高純度のα、β−クロルエチ
ルアルキルエーテルはもちろん、８０〜９０％の低純度
品を用いても反応し、得られたクロルアセクール類を精
留することにより、目的のクロルアセタール類を高純度
で冒収率に得ることが出来る。However, in the present invention, not only high-purity α,β-chloroethyl alkyl ether but also low-purity products of 80 to 90% can be used. It is possible to obtain chloroacetals of high purity and in good yields.
本発明のα、β−クロルエチルアルキルエーテルとアル
コールの脱塩酸反応は通常アルコールと脱塩酸剤の混合
物にα、β−クロルエチルアルキルエーテルを滴下し、
発生する反応熱を冷却しながら反応するが、反応の態様
はこの方法に限定するものではない。例えばα、β−ク
ロルエチルアルキルエーテルとアルコールの混合物に脱
塩酸剤を滴下する方法、不活性溶媒と脱塩酸剤の混合物
にα、β−クロルエチルアルキルエーテルとアルコール
の混合物を滴下する等の方法も可能である。The dehydrochlorination reaction of α,β-chloroethyl alkyl ether and alcohol in the present invention is usually carried out by dropping α,β-chloroethyl alkyl ether into a mixture of alcohol and a dehydrochlorination agent.
Although the reaction is carried out while cooling the generated reaction heat, the mode of the reaction is not limited to this method. For example, a method of dropping a dehydrochlorination agent into a mixture of α,β-chloroethyl alkyl ether and alcohol, a method of dropping a mixture of α,β-chloroethyl alkyl ether and alcohol into a mixture of an inert solvent and a dehydrochlorination agent, etc. is also possible.
又本発明ではα、β−クロルエチルアルキルエーテルの
アルキル基と異るアルキル基を有するアルコールを反応
するととにより、非対称のアルキル基を有するアセター
ル類の製造も可能である。例エバα、β−クロルエテル
エチルエーテルとメチルアルコールを反応することによ
りクロルアセトアルデヒド メチル エテルアセタール
が得られる。In addition, in the present invention, it is also possible to produce acetals having asymmetric alkyl groups by reacting the alkyl group of α,β-chloroethyl alkyl ether with an alcohol having a different alkyl group. EXAMPLE Chloracetaldehyde methyl ether acetal is obtained by reacting Eva α,β-chloroethyl ethyl ether with methyl alcohol.
本発明に使用される脱塩酸剤としては、トリエチルアミ
ン、トリブチルアミン、ピリジン等の第三級アミン類が
ある。The dehydrochlorination agent used in the present invention includes tertiary amines such as triethylamine, tributylamine, and pyridine.
本発明の脱塩酸反応はα、β−クロルエチルアルキルエ
ーテルの分解を抑制するため、−２０〜３０℃、好まし
くは０〜１０℃で行なわれる。The dehydrochlorination reaction of the present invention is carried out at -20 to 30°C, preferably 0 to 10°C, in order to suppress the decomposition of α,β-chloroethyl alkyl ether.
又α、β−クロルエチルアルキルニーテルトアルコール
のモル比ハ１．０〜１．２モル倍、α、β−クロルエチ
ルアルキルエーテルと脱塩酸剤のモル比は１．０〜１．
３モル倍が好ましい。The molar ratio of α, β-chloroethyl alkyl nitrate alcohol is 1.0 to 1.2 times by mole, and the molar ratio of α, β-chloroethyl alkyl ether to the dehydrochlorination agent is 1.0 to 1.
3 times the mole is preferable.
α、β−クロルエチルアルキルエーテルとアルコールの
反応で副生ずる第３級アミン塩酸塩はアルカリ水を加え
て中和後、遊離したアミンを分液するか又は溶媒抽出に
より回収し、次の脱塩酸反応に再使用できる。The tertiary amine hydrochloride produced as a by-product in the reaction of α,β-chloroethyl alkyl ether and alcohol is neutralized by adding alkaline water, and then the liberated amine is separated or recovered by solvent extraction and used for the next dehydrochlorination process. Can be reused for reactions.
本発明のクロルアセタール類は具体的には、例えばクロ
ルアセトアルデヒドジメチルアセタール。Specifically, the chloracetals of the present invention include, for example, chloroacetaldehyde dimethyl acetal.
クロルアセトアルデヒドジエチルアセタール、ジクロル
アセトアルデヒドジメチルアセタール、ジクロルアセト
アルデヒドジエチルアセタール等である。These include chloracetaldehyde diethylacetal, dichloroacetaldehyde dimethyl acetal, dichloroacetaldehyde diethylacetal, and the like.
（発明の効果）
α、β−クロルエチルアルキルニーテルトアルコールの
脱塩酸反応により高収率に高純度のクロルアセクール類
が得られる。(Effects of the Invention) Chloracecures of high purity can be obtained in high yield through the dehydrochlorination reaction of α,β-chloroethyl alkylnitrate alcohol.
又α、β−クロルエチルアルキルニーテルト異ルアルア
ルキル基ルコールを使用することにより非対称のアルキ
ル基を有するアセタール類の合成を可能にした。Furthermore, by using α,β-chloroethylalkylnitate heteroralalkyl group alcohol, it has become possible to synthesize acetals having an asymmetric alkyl group.
（実施例） 実施例中、Ｙは反応収率 ｙ／は精製後の収率を表す。(Example) In the examples, Y represents the reaction yield, and y/ represents the yield after purification.
実施例−１クロルアセトアルデヒドジエチルアセタール
の合成
攪拌機、温度計、還流冷却器及び滴下ｐ斗を備、ｔｉ２
Ａ’セパラブルフラスコにベンゼン３００ｇ、トリエチ
ルアミン３６４ｇ、エタノール１３８ｇを仕込み、５〜
１０℃を保ちながら純度９７．４％のα、β−ジクロル
エチルエチルエーテル４２９，９を２時間で滴下した。Example-1 Synthesis of chloroacetaldehyde diethyl acetal Equipped with a stirrer, a thermometer, a reflux condenser and a dropping pouch, ti2
A' Separable flask was charged with 300 g of benzene, 364 g of triethylamine, and 138 g of ethanol.
α,β-Dichloroethyl ethyl ether 429.9 with a purity of 97.4% was added dropwise over 2 hours while maintaining the temperature at 10°C.
次に５％塩酸水約４２０ｇを５〜１０℃で加え、未反応
トリエチルアミンを塩酸塩とした後、静置分液し、ベン
ゼン層７３９Ｉを得た。ベンゼン層のクロルアセトアル
デヒドジエチルアセタールは５９．９％であった。（Ｙ
−９９３％）
ベンゼン層を精留し、７５〜ｂ
の留分に純度９９．２％のクロルアセトアルデヒドジエ
チルアセタール４３９ｇを得た（Ｙ’＝９７．７％）。Next, about 420 g of 5% hydrochloric acid water was added at 5 to 10° C. to convert unreacted triethylamine into a hydrochloride salt, and the mixture was allowed to stand still for liquid separation to obtain benzene layer 739I. The content of chloroacetaldehyde diethyl acetal in the benzene layer was 59.9%. (Y
-993%) The benzene layer was rectified to obtain 439 g of chloroacetaldehyde diethyl acetal with a purity of 99.2% in the fraction 75-b (Y'=97.7%).
実施例−２クロルアセトアルデヒドジメチルアセタール
の合成
実施例−１と同様の反応器にベンゼン３００ｇとメタノ
ール１０６ｇ、トリエチルアミン３６４Ｉを仕込み、５
〜１０℃を保ちながら純度９４．７％のα、β−ジクロ
ルエチルメチルエーテル４．０９Ｉを２時間で滴下した
。次に５％塩酸水約４２０１を加え、未反応トリエチル
アミンを塩酸塩とした後、静置分液しベンゼン層６５９
ｇを得た。有機層のクロルアセトアルデヒドジメチルア
セタールは５６．０％であった。（Ｙ＝９８．８％）ベ
ンゼン層を精留し、１１０〜ｂ
ｍｙｎＨｇの留分に純度９９，４％のクロルアセトアル
デヒドジメチルアセタール３６５Ｊを得た。（ｙ／二９
７．１％）
実施例−３クロルアセトアルデヒドエチルメチルアセタ
ールの合成
実施例−１と同様の反応器にベンゼン３００ ｇ。Example 2 Synthesis of chloroacetaldehyde dimethyl acetal 300 g of benzene, 106 g of methanol, and 364 I of triethylamine were charged into the same reactor as in Example 1.
While maintaining the temperature at ~10°C, 4.09 I of α,β-dichloroethyl methyl ether with a purity of 94.7% was added dropwise over 2 hours. Next, 5% hydrochloric acid water was added to convert unreacted triethylamine into hydrochloride, and the liquid was separated by standing to form a benzene layer.659
I got g. Chloracetaldehyde dimethyl acetal in the organic layer was 56.0%. (Y=98.8%) The benzene layer was rectified to obtain 365J of chloroacetaldehyde dimethyl acetal with a purity of 99.4% in a fraction of 110 to b mynHg. (y/29
7.1%) Example 3 Synthesis of chloroacetaldehyde ethyl methyl acetal 300 g of benzene was placed in the same reactor as in Example 1.
メタノール１００ｇ、トリエチルアミン３６４ｇを仕込
み、５〜１０℃を保持しながら純度９７４％のα、β−
ジクロルエチルエチルエーテル４．２９Ｉを２時間で滴
下した。引続き５〜１０℃で５％塩酸水４２０ｇを加え
、過剰のトリエチルアミンを塩酸塩とした後静置分液し
ベンゼン層６９４ｇを得た。ベンゼン層のクロルアセト
アルデヒドエチルメチルアセタールは５７．５％であっ
た。（ｙ＝９８．６％）
ヘンセン層ヲ蒸留ｔ、、 ６３〜ｂ
の留分ニ純度９９５％のクロルアセトアルデヒドエテル
メチルアセクール３９６ｇを得た（Ｙ′二９７．４％）
。Prepared 100g of methanol and 364g of triethylamine, and while maintaining the temperature at 5~10℃, α, β-
4.29 I of dichloroethyl ethyl ether was added dropwise over 2 hours. Subsequently, 420 g of 5% hydrochloric acid water was added at 5 to 10° C. to convert excess triethylamine into hydrochloride, and the mixture was allowed to stand still for liquid separation to obtain 694 g of a benzene layer. The content of chloroacetaldehyde ethyl methyl acetal in the benzene layer was 57.5%. (y=98.6%) Distillation of the Hensen layer t, 396 g of chloroacetaldehyde ether methyl acecool with a purity of 995% was obtained from fractions 63-b (Y'2 97.4%)
.
実施例−４ジクロルアセトアルデヒドジエチルアセクー
ルの合成
実施例−１と同様の３ノ反応器にトルエン４００１、エ
タノール１５９１ トリエチルアミン３９４ｙを仕込
み、５〜１０℃に保持し々から純度９５．３％のα、β
、β−トリクロルエチルエーテル５８９ｇを２時間で滴
下した。引続き５〜１０℃で５％塩酸水６６０．９を加
え過剰のトリエチルアミンを塩酸塩とした後、静置、分
液しトルエン層９１７ｇを得た。トルエン層のジクロル
アセトアルデヒドジエチルアセクールは５５．６％であ
った（Ｙ＝９９．５％）。Example 4 Synthesis of dichloroacetaldehyde diethyl acecool Toluene 4001, ethanol 1591, and triethylamine 394y were charged into three reactors similar to those in Example 1, and kept at 5 to 10°C to produce α with a purity of 95.3%. ,β
, 589 g of β-trichloroethyl ether was added dropwise over 2 hours. Subsequently, 660.9 g of 5% aqueous hydrochloric acid was added at 5 to 10° C. to convert excess triethylamine into hydrochloride, and the mixture was allowed to stand still and separated to obtain 917 g of a toluene layer. Dichloroacetaldehyde diethyl acecool in the toluene layer was 55.6% (Y=99.5%).
トルエン層を蒸留し、８５〜ｂ
の留分に純度９８．９％のジクロルアセトアルデヒドジ
エチルアセタール５２９Ｉを得た（Ｙ’＝９８．３％）
。The toluene layer was distilled to obtain dichloroacetaldehyde diethyl acetal 529I with a purity of 98.9% in the fraction 85-b (Y' = 98.3%).
.
Claims (2)
ルエーテルと、アルコールの反応により一般式▲数式、
化学式、表等があります▼（ここでＸ＿１およびＸ＿２
は水素又は塩素を、Ｒ及びＲ＿１はＣ＿１〜Ｃ＿４のア
ルキル基を示す）で表わされるクロルアセタール類を製
造することを特徴とするクロルアセタール類の製造法。(1) In the presence of a dehydrochlorination agent, the reaction between α,β-chloroethyl alkyl ether and alcohol results in the general formula ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (Here, X_1 and X_2
represents hydrogen or chlorine, and R and R_1 represent C_1 to C_4 alkyl groups.
範囲第一項記載の方法。(2) The method according to claim 1, wherein a tertiary amine is used as the dehydrochlorination agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12225487A JPS63287739A (en) | 1987-05-19 | 1987-05-19 | Production of chloroacetals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12225487A JPS63287739A (en) | 1987-05-19 | 1987-05-19 | Production of chloroacetals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63287739A true JPS63287739A (en) | 1988-11-24 |
Family
ID=14831400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12225487A Pending JPS63287739A (en) | 1987-05-19 | 1987-05-19 | Production of chloroacetals |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63287739A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304687A (en) * | 1989-12-19 | 1994-04-19 | Farmitalia Carlo Erba S.R.L. | Morpholinyl derivatives of doxorubicin and process for their preparation |
| JP2010530859A (en) * | 2007-06-22 | 2010-09-16 | サルティゴ・ゲーエムベーハー | Process for producing 2-hydroxyacetal and the corresponding 2-hydroxyalkanal |
-
1987
- 1987-05-19 JP JP12225487A patent/JPS63287739A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5304687A (en) * | 1989-12-19 | 1994-04-19 | Farmitalia Carlo Erba S.R.L. | Morpholinyl derivatives of doxorubicin and process for their preparation |
| JP2010530859A (en) * | 2007-06-22 | 2010-09-16 | サルティゴ・ゲーエムベーハー | Process for producing 2-hydroxyacetal and the corresponding 2-hydroxyalkanal |
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