JPH0211536A - Preparation of 2,4-dihydroxyacetophenone - Google Patents
Preparation of 2,4-dihydroxyacetophenoneInfo
- Publication number
- JPH0211536A JPH0211536A JP63165377A JP16537788A JPH0211536A JP H0211536 A JPH0211536 A JP H0211536A JP 63165377 A JP63165377 A JP 63165377A JP 16537788 A JP16537788 A JP 16537788A JP H0211536 A JPH0211536 A JP H0211536A
- Authority
- JP
- Japan
- Prior art keywords
- resorcinol
- dihydroxyacetophenone
- reaction
- approximately
- zinc
- 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
- SULYEHHGGXARJS-UHFFFAOYSA-N 2',4'-dihydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1O SULYEHHGGXARJS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- KLAKIAVEMQMVBT-UHFFFAOYSA-N p-hydroxy-phenacyl alcohol Natural products OCC(=O)C1=CC=C(O)C=C1 KLAKIAVEMQMVBT-UHFFFAOYSA-N 0.000 title claims abstract description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 45
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 11
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 11
- ZZPKZRHERLGEKA-UHFFFAOYSA-N resorcinol monoacetate Chemical compound CC(=O)OC1=CC=CC(O)=C1 ZZPKZRHERLGEKA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000006276 transfer reaction Methods 0.000 claims abstract 3
- 238000000034 method Methods 0.000 claims description 23
- -1 zinc halide Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 229960001755 resorcinol Drugs 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006462 rearrangement reaction Methods 0.000 description 6
- HEJLFBLJYFSKCE-UHFFFAOYSA-N 2',3'-Dihydroxyacetophenone Chemical compound CC(=O)C1=CC=CC(O)=C1O HEJLFBLJYFSKCE-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940102001 zinc bromide Drugs 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
- Catalysts (AREA)
- 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、２．４−ジヒドロキシアセトフェノンの製造
法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an improvement in a method for producing 2,4-dihydroxyacetophenone.
〈従来の技術〉
レゾルシン化合物と低級カルボン酸をハロゲン化亜鉛の
存在下に反応させて２，４−ジヒドロキシアセトフェノ
ンを製造する方法は、従来から公知である。例えばその
具体例として、酢酸と塩化亜鉛の混合物を１４０℃まで
加熱溶解し、これにレゾルシンを加えて１５９℃まで加
熱する方法（ＯＲＧＡＮＩＣ５ＹＮＴＨＥＳＥＳ Ｃｏ
１１ｅｃｔｉｖｅ Ｖｏｌ、３，７６１頁）、塩化亜鉛
の存在下、レゾルシンと酢酸を１００〜１３０℃で反応
させる方法（特開昭５９−６５０３９号）及びレゾルシ
ンと低級カルボン酸をハロゲン化亜鉛の存在下に反応さ
せて目的とするケトンを製造する際に、反応系に脱水剤
を共存せしめる方法（特開昭６１−１７６５４８号）等
が知られている。<Prior Art> A method for producing 2,4-dihydroxyacetophenone by reacting a resorcin compound and a lower carboxylic acid in the presence of zinc halide has been conventionally known. For example, a specific example is a method in which a mixture of acetic acid and zinc chloride is heated to 140°C and dissolved, resorcinol is added thereto and heated to 159°C (ORGANIC5YNTHESES Co.
11ective Vol., p. 3, 761), a method of reacting resorcin and acetic acid at 100 to 130°C in the presence of zinc chloride (Japanese Patent Application Laid-Open No. 1983-65039), and a method of reacting resorcin and a lower carboxylic acid in the presence of zinc halide. A method is known in which a dehydrating agent is present in the reaction system when producing the desired ketone (Japanese Patent Application Laid-Open No. 176548/1983).
しかじながろ、これらいずれの方法も２．４−ジヒドロ
キシアセトフェノンの選択率、収率及ヒ純度の何れかの
面で、工業的方法として必ずしも満足できるものではな
かった。However, none of these methods was necessarily satisfactory as an industrial method in terms of selectivity, yield and purity of 2,4-dihydroxyacetophenone.
他方、レゾルシンと無水酢酸を反応させて、２゜４−ジ
ヒドロキンアセトフェノンを製造する方法において、先
ず５０〜１００℃に維持したレゾルシン酢酸溶液に、無
水酢酸を反応させてエステル化反応させ（第一段反応）
、次いで部分的に脱酢酸した中間液を１２０〜１５０℃
で硫酸により転位反応させる（第２１３Ｅ反応）による
方法が知られている（特開昭６０−２４８６４２号）し
かしながら、この方法は硫酸との加熱接触による有効成
分の炭化（タール化）により、収率を低下させるばかり
でなく、得られる２、４−ジヒドロキシアセトフェノン
は著しく着色するために精製工程が必要等、やはり工業
的製造法としては満足すべきものではなかった。On the other hand, in a method for producing 2゜4-dihydroquinacetophenone by reacting resorcin and acetic anhydride, first, a resorcin acetic acid solution maintained at 50 to 100°C is reacted with acetic anhydride to carry out an esterification reaction (the first stage reaction)
Then, the partially deaceticated intermediate solution was heated to 120-150°C.
A method is known in which a rearrangement reaction is carried out with sulfuric acid (No. 213E reaction) (Japanese Patent Application Laid-Open No. 60-248642). However, in this method, the yield is reduced due to carbonization (tarring) of the active ingredient due to heating contact with sulfuric acid. In addition, the obtained 2,4-dihydroxyacetophenone was markedly colored and required a purification step, so that it was still unsatisfactory as an industrial production method.
〈発明が解決しようとする課題〉
本発明者らは、前記従来法における欠点を解決すべく鋭
意検討の結果、レゾルシンを酢酸溶媒下無水酢酸と反応
させて一酢酸レゾルシンとしたのち、ハロゲン化亜鉛の
存在下に、転移反応させるという手段を採用することに
よって、２．４−ジヒドロキシアセトフェノンの収率を
飛躍的に向上させ、かつ着色のない２．４−ジヒドロキ
シアセトフェノンが製造できることを見い出し、本発明
を完成した。<Problems to be Solved by the Invention> As a result of intensive studies to solve the drawbacks of the conventional methods, the present inventors reacted resorcin with acetic anhydride in an acetic acid solvent to produce resorcin monoacetate, and then reacted it with zinc halide. It has been discovered that the yield of 2,4-dihydroxyacetophenone can be dramatically improved and color-free 2,4-dihydroxyacetophenone can be produced by adopting a method of rearrangement reaction in the presence of completed.
く課題を解決するための手段〉
すなわち、本発明は、レゾルシンを酢酸溶媒下、無水酢
酸と反応させて一酢酸レゾルシンとする工程（第１段反
応）
生成した一酢酸レゾルシンを、ハロゲン化亜鉛の存在下
、転移反応させる工程（第２段反応）からなることを特
徴とする２、４−ジヒドロキシアセトフェノンの製造法
である。Means for Solving the Problems> That is, the present invention comprises a step of reacting resorcin with acetic anhydride in an acetic acid solvent to produce resorcin monoacetate (first stage reaction), reacting the produced resorcin monoacetate with zinc halide, This is a method for producing 2,4-dihydroxyacetophenone, characterized by comprising a step of carrying out a rearrangement reaction (second stage reaction) in the presence of 2,4-dihydroxyacetophenone.
以下、本発明の方法を更に具体的に説明する。The method of the present invention will be explained in more detail below.
本発明方法は、第１段反応（エステル化反応）及び第２
段反応（転位反応）を経ることを特徴とするものである
。The method of the present invention comprises a first stage reaction (esterification reaction) and a second stage reaction.
It is characterized by undergoing a step reaction (rearrangement reaction).
ここで、第１段反応（エステル化反応）における酢酸の
使用量は、通常レゾルシンに対し約０゜２〜１重量倍で
ある。もちろんそれ以上多量に酢酸を使用しても２．４
−ジヒドロキシアセトフェノンの品質・収率には悪影響
を及ぼさないが、酢酸を無水で回収リサイクルする処理
は、工業的には煩雑となるので、むしろ酢酸は、レゾル
シンに対して約０．２〜１重量倍程度使用し、回収しな
い方法が工業的製造プロセスとしては好ましい。Here, the amount of acetic acid used in the first stage reaction (esterification reaction) is usually about 0.2 to 1 times the weight of resorcinol. Of course, even if acetic acid is used in a larger amount than that, the
- Although it does not have a negative effect on the quality and yield of dihydroxyacetophenone, the process of anhydrous recovery and recycling of acetic acid is industrially complicated, so acetic acid should be about 0.2 to 1 weight per resorcinol. A method that uses about twice as much and does not recover is preferable as an industrial manufacturing process.
また、無水酢酸の使用量はレゾルシンに対して約０．２
〜１モル倍、好ましくは０．３〜０．８モル倍である。In addition, the amount of acetic anhydride used is approximately 0.2 to resorcinol.
~1 mol times, preferably 0.3 to 0.8 mol times.
ここでレゾルシンに対して無水酢酸を更に過剰に用いる
と、ジアシル体の比率が増え、２．４−ジヒドロキシア
セトフェノンの品質・収率が低下する傾向を示す。If acetic anhydride is used in excess of resorcinol, the ratio of diacyl forms increases, and the quality and yield of 2,4-dihydroxyacetophenone tend to decrease.
該エステル化反応は、約３０〜１００℃の温度範囲、好
ましくは４０〜８０℃で行われる。得られた反応液はな
んら処理することなく次の工程へ移行することが好まし
い。The esterification reaction is carried out at a temperature range of about 30-100°C, preferably 40-80°C. It is preferable that the obtained reaction solution is transferred to the next step without any treatment.
次に、第２段反応（転位反応）におけるハロゲン化亜鉛
の具体例としては、フッ化亜鉛、塩化亜鉛、臭化亜鉛、
ヨウ化亜鉛があり、とくに塩化亜鉛が好ましく用いられ
る。Next, specific examples of zinc halides in the second stage reaction (rearrangement reaction) include zinc fluoride, zinc chloride, zinc bromide,
Zinc iodide is used, and zinc chloride is particularly preferably used.
ここで用いるハロゲン化亜鉛の使用量は、通常レゾルシ
ンに対して約０．２〜１モル倍、好ましくは０．３〜０
．８モル倍使用される。もちろん多量にハロゲン化亜鉛
を使用しても目的とする２、４−ジヒドロキシアセトフ
ェノンの品質・収率に悪影響を及ぼさないが、非経済的
である。又ハロゲン化亜鉛の添加量が少ない場合は、ジ
ヒドロキシアセトフェノンへの転化率が低くなり、好ま
しくない傾向を示す。The amount of zinc halide used here is usually about 0.2 to 1 mole relative to resorcinol, preferably 0.3 to 0.
．． 8 moles are used. Of course, even if a large amount of zinc halide is used, the quality and yield of the target 2,4-dihydroxyacetophenone are not adversely affected, but it is uneconomical. Moreover, when the amount of zinc halide added is small, the conversion rate to dihydroxyacetophenone becomes low, showing an unfavorable tendency.
転位反応は、約９０〜１４０℃の温度範囲、好ましくは
１００〜１３０℃で行われる。ここで反応温度９０℃以
下ではジヒドロキシアセトフェノンへの転化率が低くな
り、又１４０℃以上ではジヒドロキシアセトフェノンの
着色が著しくなり、好ましくない傾向を示す。The rearrangement reaction is carried out at a temperature range of about 90-140°C, preferably 100-130°C. Here, if the reaction temperature is 90° C. or lower, the conversion rate to dihydroxyacetophenone will be low, and if the reaction temperature is 140° C. or higher, the coloring of dihydroxyacetophenone will become significant, showing an unfavorable tendency.
本発明の各段反応に供するレゾルシン、酢酸、無水酢酸
及びハロゲン化亜鉛は、いづれも実質的に無水であるこ
とが好ましい。It is preferable that the resorcinol, acetic acid, acetic anhydride, and zinc halide used in each step of the reaction of the present invention are all substantially anhydrous.
本発明の方法によって得られた反応液の取り出しは、従
来公知の種々の方法が採用され、例えば水もしくは酸を
加えて分解させ、次いで冷却し、２．４−ジヒドロキシ
アセトフェノンを晶析させ、濾過及び乾燥を経て製品化
される。又、より高品質のものが必要である場合には、
さらに水再結晶等のｍ製処理を行なうことができる。The reaction solution obtained by the method of the present invention can be taken out by various conventionally known methods, such as adding water or acid to decompose it, cooling it, crystallizing 2,4-dihydroxyacetophenone, and filtering it. After drying, it is made into a product. Also, if you need something of higher quality,
Furthermore, m-manufacturing treatments such as water recrystallization can be performed.
〈発明の効果〉
本発明の方法によれば、従来公知の技術に比較して、高
収率・高純度で目的とする２、４−ジヒドロキシアセト
フェノンを製造することができ、特に反応後の蒸留・再
結晶などの煩雑は操作を避けることができ、しかも実質
的に着色のない高品質の目的物が得られる。<Effects of the Invention> According to the method of the present invention, the desired 2,4-dihydroxyacetophenone can be produced in higher yield and purity than conventionally known techniques. - Complicated operations such as recrystallization can be avoided, and high-quality target products with virtually no coloration can be obtained.
この様にして得られた２、４−ジヒドロキシアセトフェ
ノンは、ファインケミカル中間体、医薬、農薬、感光材
料、香料、樹脂等の原料として有利に供給される。The 2,4-dihydroxyacetophenone thus obtained is advantageously supplied as a raw material for fine chemical intermediates, medicines, agricultural chemicals, photosensitive materials, fragrances, resins, and the like.
〈実施例〉
以下に実施例及び比較例を挙げて、本発明をさらに具体
的に説明する。なお、実施例中の部及び％は特に゛断り
のない限り重量基準である。<Example> The present invention will be described in more detail below with reference to Examples and Comparative Examples. In addition, parts and percentages in the examples are based on weight unless otherwise specified.
実施例１
撹拌装置、温度計、冷却管を装着した４ツロフラスコに
レゾルシン１００１１’ｌＳ、酢酸３５部、無水酢酸６
０部を仕込み、６０℃まで昇温し、その温度で約１時間
撹拌する。次いで塩化亜鉛８０都を仕込み、１２０℃ま
で１時間で昇温し、同温度で約１時間保温撹拌する。ガ
スクロマトグラフィーにより原料レゾルシンおよび一酢
酸レゾルシンの消失を確認後、１００℃まで冷却し、１
８％塩酸水４００部を滴下注入する。その後、３０℃ま
で冷却し、２．４−ジヒドロキシアセトフェノンを晶析
する。スラリーを濾過し、９％塩酸水１７０部と水１４
０１％で洗浄し、次いで乾燥して白色の２．４−ジヒド
ロキシアセトフェノン１２７部を得た。レゾルシンに対
する収１ｔ９２．３％であり、純度は９９．７％であっ
た。融点は１４６〜１４７℃であった。Example 1 Resorcinol 10011'lS, 35 parts of acetic acid, and 6 parts of acetic anhydride were placed in a 4-tube flask equipped with a stirrer, a thermometer, and a cooling tube.
0 part was charged, the temperature was raised to 60°C, and the mixture was stirred at that temperature for about 1 hour. Next, 80 tons of zinc chloride were charged, the temperature was raised to 120°C over 1 hour, and the mixture was stirred at the same temperature for about 1 hour. After confirming the disappearance of the raw material resorcin and monoacetate resorcin by gas chromatography, it was cooled to 100°C and
Inject 400 parts of 8% hydrochloric acid solution dropwise. Thereafter, the mixture is cooled to 30° C. and 2,4-dihydroxyacetophenone is crystallized. Filter the slurry, add 170 parts of 9% hydrochloric acid and 14 parts of water.
01% and then dried to obtain 127 parts of white 2,4-dihydroxyacetophenone. The yield was 92.3% based on resorcinol, and the purity was 99.7%. The melting point was 146-147°C.
実施例２〜８
下記表−１に示す条件以外は実施例１と同様にして反応
させて、表−１の結果を得た。Examples 2 to 8 The reaction was carried out in the same manner as in Example 1 except for the conditions shown in Table 1 below, and the results shown in Table 1 were obtained.
表−１
ｘｉ レゾルシン１モルに対する塩化亜鉛のモル数仕
込レゾルシンに対して得られた２、 ４−ジヒドロキ
シアセトフェノンの収率（％）零２
比較例１
塩化亜鉛のかわりに９８％硫酸２部を使用する以外は実
施例１と全く同様にして実験を行ったところ、得られた
２、４−ジヒドロキシアセトフェノンは赤褐色に着色し
ており、収率は６８．５％であった。Table-1 xi Number of moles of zinc chloride per mole of resorcinol Yield (%) of 2,4-dihydroxyacetophenone obtained from charged resorcinol 0 2 Comparative Example 1 2 parts of 98% sulfuric acid was used in place of zinc chloride An experiment was carried out in the same manner as in Example 1, except for the following. The obtained 2,4-dihydroxyacetophenone was colored reddish brown, and the yield was 68.5%.
比較例２
撹拌装置、温度計、冷却管を装着した４ツロフラスコに
、酢酸１１１部、塩化亜鉛１１１部及びレゾルシン４５
部を仕込み、１３０℃まで昇温し、その温度で０．５時
間かけて無水酢酸４３部を添加した。Comparative Example 2 111 parts of acetic acid, 111 parts of zinc chloride, and 45 parts of resorcinol were added to a 4-tube flask equipped with a stirrer, a thermometer, and a cooling tube.
The mixture was heated to 130°C, and 43 parts of acetic anhydride was added at that temperature over 0.5 hours.
同温度で０．５時間保温撹拌する。その後、１８％塩酸
水３３０部を加えて、３９℃まで冷却して晶析し、濾過
、７％塩酸１３０部で洗浄し、乾燥し、４２．７５部の
粗２．４−ジヒドロキンアセトフェノンを得た。レゾル
シンに対する枢収率は５５，５％（純度８０．７９ ％
）であった。Stir at the same temperature for 0.5 hour. Thereafter, 330 parts of 18% hydrochloric acid solution was added, and the mixture was cooled to 39°C to crystallize, filtered, washed with 130 parts of 7% hydrochloric acid, and dried to obtain 42.75 parts of crude 2,4-dihydroquine acetophenone. Obtained. The central yield for resorcinol is 55.5% (purity 80.79%)
)Met.
Claims (8)
一酢酸レゾルシンとする工程（第１段反応）生成した一
酢酸レゾルシンを、ハロゲン化亜鉛の存在下、転移反応
させる工程（第２段反応）からなることを特徴とする２
，４−ジヒドロキシアセトフェノンの製造法。(1) A step in which resorcinol is reacted with acetic anhydride in an acetic acid solvent to form resorcinol monoacetate (first stage reaction) A step in which the produced resorcinol monoacetate is subjected to a transfer reaction in the presence of zinc halide (second stage reaction) ) is characterized by consisting of 2
, 4-dihydroxyacetophenone manufacturing method.
）に記載の方法。(2) Claim (1) in which the first stage reaction is carried out at about 30 to 100°C.
).
に記載の方法。(3) Claim (2) in which the first stage reaction is carried out at about 40 to 80°C.
The method described in.
）又は（２）に記載の方法。(4) Claim (1) in which the second stage reaction is carried out at about 90 to 140°C.
) or the method described in (2).
４）に記載の方法。(5) Claim (
The method described in 4).
酸を用いる請求項（１）〜（５）のいずれかに記載の方
法。(6) The method according to any one of claims (1) to (5), wherein acetic anhydride is used in an amount of about 0.2 to 1 mole relative to resorcinol.
（６）のいずれかに記載の方法。(7) Claims (1)-- wherein the zinc halide is zinc chloride.
The method described in any of (6).
鉛を用いる請求項（１）〜（５）のいずれかに記載の方
法。(8) The method according to any one of claims (1) to (5), wherein zinc chloride is used in an amount of about 0.2 to 1 times the mole of resorcinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63165377A JP2560431B2 (en) | 1988-06-30 | 1988-06-30 | Method for producing 2,4-dihydroxyacetophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63165377A JP2560431B2 (en) | 1988-06-30 | 1988-06-30 | Method for producing 2,4-dihydroxyacetophenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0211536A true JPH0211536A (en) | 1990-01-16 |
| JP2560431B2 JP2560431B2 (en) | 1996-12-04 |
Family
ID=15811219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63165377A Expired - Fee Related JP2560431B2 (en) | 1988-06-30 | 1988-06-30 | Method for producing 2,4-dihydroxyacetophenone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2560431B2 (en) |
-
1988
- 1988-06-30 JP JP63165377A patent/JP2560431B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2560431B2 (en) | 1996-12-04 |
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