JP2933955B2 - Purification method of chroman compounds - Google Patents
Purification method of chroman compoundsInfo
- Publication number
- JP2933955B2 JP2933955B2 JP29116789A JP29116789A JP2933955B2 JP 2933955 B2 JP2933955 B2 JP 2933955B2 JP 29116789 A JP29116789 A JP 29116789A JP 29116789 A JP29116789 A JP 29116789A JP 2933955 B2 JP2933955 B2 JP 2933955B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- chroman
- formula
- purification method
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Pyrane Compounds (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は農薬製造のための中間体として有用なクロマ
ン類化合物の工業的有利な精製方法に関するものであ
る。Description: TECHNICAL FIELD The present invention relates to an industrially advantageous method for purifying chroman compounds useful as intermediates for producing agricultural chemicals.
さらに詳しくは、本発明は一般式〔Ｉ〕 （式中、R1ないしR5は同一又は相異なって水素原子又は
低級アルキル基を示し、R6は低級アルキル基を示し、R2
とR5は両者が結合して炭素数２ないし３のアルキレン基
を形成してもよい。） で示されるクロマン類化合物を塩基の共存下に蒸留する
ことを特徴とするクロマン類化合物の精製方法を提供す
るものである。More specifically, the present invention provides a compound represented by the general formula [I] (Wherein, to no R 1 R 5 represents a hydrogen atom or a lower alkyl group the same or different, R 6 represents a lower alkyl group, R 2
And R 5 may combine with each other to form an alkylene group having 2 or 3 carbon atoms. The present invention provides a method for purifying a chroman compound, which comprises distilling the chroman compound represented by the formula (1) in the presence of a base.
前記一般式〔Ｉ〕で示されるクロマン類化合物農薬製
造のための中間体として有用な公知化合物であり、この
製造方法は例えば特開昭63−203677号及び特願平１−16
9947号（特開平３−38584号）の明細書に記載されてい
る。Chromane compounds represented by the above general formula [I] are known compounds useful as intermediates for the production of pesticides. This production method is described in, for example, JP-A-63-203677 and Japanese Patent Application No. 1-16.
No. 9947 (JP-A-3-38584).
これらに記載されている製法では、反応終了後反応混
合物を飽和NaHCO3水溶液で中和した後有機溶媒で抽出
し、溶媒留去したものをシリカゲルカラムクロマトグラ
フィーで精製し目的物を得ている。In the production methods described therein, after completion of the reaction, the reaction mixture is neutralized with a saturated aqueous solution of NaHCO 3 , extracted with an organic solvent, and the solvent is distilled off and purified by silica gel column chromatography to obtain the desired product.
クロマン類化合物を工業的規模で製造する場合、カラ
ムクロマトグラフィーによる精製方法はコスト面で問題
があった。When producing chroman compounds on an industrial scale, the purification method by column chromatography has a problem in cost.
そこで本発明者等はクロマン類化合物の工業的有利な
精製方法の確立を目的として、蒸留による精製方法を種
々検討した。Therefore, the present inventors have studied various purification methods by distillation for the purpose of establishing an industrially advantageous purification method for chroman compounds.
その結果、工業的に一般に行われている減圧蒸留では
反応混合物から目的物を効率良く回収出来ないのに対
し、蒸留を塩基化合物の共存下に行うことにより目的物
を著しく高純度且つ高回収率で分離採取し得ることを見
出し、本発明を完成した。As a result, the desired product cannot be efficiently recovered from the reaction mixture by vacuum distillation, which is generally performed on an industrial scale. Thus, the present invention was completed.
本発明は、一般式〔ｌ〕 （式中、R1R5はないし同一又は相異なって水素原子又は
低級アルキル基を示し、R6は低級アルキル基を示し、R2
とR5は両者が結合して炭素数２ないし３のアルキレン基
を形成してもよい。） で示されるクロマン類化合物を含む混合物を塩基化合物
の共存下に蒸留することを特徴とするクロマン類化合物
の製造方法に関するものである。The present invention has the general formula [l]: (Wherein, R 1 R 5 do not represent a hydrogen atom or a lower alkyl group the same or different, R 6 represents a lower alkyl group, R 2
And R 5 may combine with each other to form an alkylene group having 2 or 3 carbon atoms. A method for producing a chroman compound, comprising distilling a mixture containing a chroman compound represented by the formula (1) in the presence of a base compound.
本発明によれば、工業的有利に〔Ｉ〕式のクロマン類
化合物を高回収率で精製することが出来る。According to the present invention, chroman compounds of the formula [I] can be purified industrially at a high recovery rate.
蒸留の際共存させる塩基化合物は〔Ｉ〕式のクロマン
類化合物の加熱時の脱アルコール反応やオリゴマー化反
応を抑制し、目的物の回収率を高める作用を示す。The base compound coexisting during the distillation has an effect of suppressing the dealcoholation reaction or oligomerization reaction of the chroman compound of the formula [I] at the time of heating and increasing the recovery of the target compound.
本発明に利用する塩基化合物としては、LiOH,KOH,NaO
H,Be（OH）2,Mg（OH）2,Ca（OH）２などの水酸化物、Na
CO3,NaHCO3,CH3CO2Na,Na3PO4などの弱酸と強塩基の塩、
高沸点のトリアルキルアミン類、ジアルキルアニリン類
などが例示される。As the basic compound used in the present invention, LiOH, KOH, NaO
Hydroxides such as H, Be (OH) 2 , Mg (OH) 2 , Ca (OH) 2 , Na
Salts of weak acids and strong bases, such as CO 3 , NaHCO 3 , CH 3 CO 2 Na, Na 3 PO 4
Examples thereof include high boiling trialkylamines and dialkylanilines.
これらは単独又は２種類以上を組合わせて利用するこ
とが出来る。These can be used alone or in combination of two or more.
通常、KOHおよびNaOHが好適に利用される。 Usually, KOH and NaOH are preferably used.
塩基化合物は、そのまま又は適当な溶媒に溶解して溶
液として添加することが出来る。The base compound can be added as it is or after dissolving in a suitable solvent as a solution.
塩基の添加量はクロマン類に対して、強塩基化合物の
場合には0.0001〜５倍モル、好ましくは0.01〜１倍モ
ル、弱塩基の場合には0.001〜10倍モル、好ましくは0.0
1〜２倍モルである。The amount of the base to be added is 0.0001 to 5 times, preferably 0.01 to 1 times, in the case of a strong base compound and 0.001 to 10 times, preferably 0.01 to 1 time in the case of a weak base, the chromans.
It is 1 to 2 times mol.
蒸留温度は低いほど脱アルコール及びオリゴマー化を
起こしにくく、通常約200℃以下が好ましい。As the distillation temperature is lower, dealcoholation and oligomerization are less likely to occur, and usually about 200 ° C. or lower is preferable.
以下、〔Ｉ〕式のクロマン化合物の熱分解が塩基化合
物の添加により抑制されることを説明するため試験例を
示す。Hereinafter, test examples will be described to explain that the thermal decomposition of the chroman compound of the formula [I] is suppressed by the addition of the basic compound.
試験例 2,4,4−トリメチル−２−メトキシ−７−ヒドロキシ
クロマン0.1gを試験管に入れ、これに1N−NaOH水溶液10
u（0.02倍モル）を添加した試料と、対照のためのNaO
H無添加の試料を準備し、それぞれ150℃に加熱し、その
温度で２時間保持した後内容物を分析した。Test Example 0.1 g of 2,4,4-trimethyl-2-methoxy-7-hydroxychroman was placed in a test tube, and a 1N-NaOH aqueous solution 10 was added thereto.
u (0.02 molar) and NaO for control
Samples without H were prepared, heated to 150 ° C. and kept at that temperature for 2 hours, and the contents were analyzed.
その結果、NaOH無添加の試料は脱メタノール、オリゴ
マー化を起こ１の純度が著しく低下したのに対し、NaOH
を添加した試料は純度の低下が少なく、脱メタノール体
の生成も少なかった。As a result, the sample without addition of NaOH caused methanol removal and oligomerization, and the purity of 1 was remarkably reduced.
The sample to which was added had a small decrease in purity and a small amount of a methanol-free product.
本試験の成績は、第１表に示すとおりである。 The results of this test are shown in Table 1.
〔発明の効果〕 本発明により、農薬製造の中間体として有用な〔Ｉ〕
式で示されるクロマン類化合物の工業的有利な蒸留によ
る精製方法が提供された。 [Effect of the Invention] According to the present invention, [I] useful as an intermediate for the production of agrochemicals
An industrially advantageous method for purifying chroman compounds represented by the formula by distillation is provided.
従来、〔Ｉ〕式のクロマン類化合物は一部の例外を除
き殆んど全ての化合物が常温で液体であるため、再結晶
による精製が出来ず、蒸留により精製しようとすれば、
加熱により目的物が脱アルコール反応を起こし、回収率
が著しく低下すること等のため、精製法として、非常に
コスト高なカラムクロマトグラフィーを採用せざる得な
かった。Conventionally, most of the chroman compounds of the formula (I) are liquid at room temperature, except for some exceptions, and cannot be purified by recrystallization.
Since the target product undergoes a dealcoholization reaction due to heating and the recovery rate is remarkably reduced, a very expensive column chromatography has to be adopted as a purification method.
このような状況の下、単に塩基化合物を共存させると
いう非常に単純な操作で〔Ｉ〕式クロマン類化合物の蒸
留による精製を可能にしたことは、蒸留が工業的に非常
に有利な精製法であることから、産業上多大のメリット
をもたらすものである。Under these circumstances, the purification of the chroman compound of formula (I) by distillation with a very simple operation of simply allowing a base compound to coexist is a purification method in which distillation is industrially very advantageous. As a result, it brings great industrial benefits.
以下に実施例及び比較例によって本発明を具体的に説
明するが、本発明は実施例のみにより限定されるもので
はない。Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited only to Examples.
実施例 500mlステンレス製オートクレーブにレゾルシン22g
（200mmol）、アセトン46g（800mmol）、メタノール64g
（2000mmol）ｇ、濃硫酸4g（40mmol）、およびトルエン
200mlを入れて密封した後、100℃で４時間反応させた。Example 22 g of resorcinol in a 500 ml stainless steel autoclave
(200 mmol), acetone 46 g (800 mmol), methanol 64 g
(2000 mmol) g, concentrated sulfuric acid 4 g (40 mmol), and toluene
After 200 ml was added and sealed, the mixture was reacted at 100 ° C. for 4 hours.
室温で冷却後反応液を飽和NaHCO3水で中和し、充分水
洗した後トルエンを減圧留去し、反応混合物55g（純度3
7％）を得た。After cooling at room temperature, the reaction solution was neutralized with saturated aqueous NaHCO 3 , washed well with water, and toluene was distilled off under reduced pressure. 55 g of the reaction mixture (purity 3
7%).
この反応混合物27.6gに3N−NaOH水溶液330μ（0.02
倍モル）を加え、４〜10mmHgの減圧下190〜202℃に加熱
して蒸留したところ緑色高粘度液体9.5g（純度86％）を
得た。このときの2,4,4−トリメチル−２−メトキシ−
７−ヒドロキシクロマン回収率は80％であった。To 27.6 g of this reaction mixture, 330 μ (0.02
The mixture was heated at 190 to 202 ° C. under reduced pressure of 4 to 10 mmHg and distilled to obtain 9.5 g (purity 86%) of a green viscous liquid. At this time, 2,4,4-trimethyl-2-methoxy-
The 7-hydroxychroman recovery was 80%.
留出物中には脱メタノール物が７％含まれていた。 The distillate contained 7% of demethanol.
比較例 実施例で使用したものと同じ2,4,4−トリメチル−２
−メトキシ−７−ヒドロキシクロマンを含む反応混合物
27.6g（純度37％）を４〜10mmHgの減圧下180〜195℃に
加熱して蒸留したところ緑色高粘度液体8.6g（純度49
％）を得た。このときの2,4,4−トリメチル−２−メト
キシ−７−ヒドロキシクロマンの回収率は41％であっ
た。Comparative Example The same 2,4,4-trimethyl-2 used in the example
Reaction mixture containing -methoxy-7-hydroxychroman
27.6 g (purity 37%) was distilled by heating to 180 to 195 ° C under reduced pressure of 4 to 10 mmHg.
%). At this time, the recovery of 2,4,4-trimethyl-2-methoxy-7-hydroxychroman was 41%.
留出物中には脱メタノール物が44％含まれていた。 The distillate contained 44% of demethanol.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木原 則昭 山口県玖珂郡和木町和木６丁目１番２号 三井石油化学工業株式会社内 (56)参考文献 特開 昭59−88479（ＪＰ，Ａ) 特開 昭63−203677（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C07D 311/00 - 311/96 ＣＡ（ＳＴＮ)────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Noriaki Kihara 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industries, Ltd. (56) References JP-A-59-88479 (JP, A) JP-A-63-203677 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C07D 311/00-311/96 CA (STN)
Claims (1)
低級アルキル基を示し、R6は低級アルキル基を示し、R2
とR5は両者が結合して炭素数２ないし３のアルキレン基
を形成してもよい。） で示されるクロマン類化合物を含む混合物を塩基化合物
の共存下に蒸留することを特徴とするクロマン類化合物
の精製方法。1. A compound of the formula [I] (Wherein, to no R 1 R 5 represents a hydrogen atom or a lower alkyl group the same or different, R 6 represents a lower alkyl group, R 2
And R 5 may combine with each other to form an alkylene group having 2 or 3 carbon atoms. A method for purifying a chroman compound, comprising distilling a mixture containing the chroman compound represented by the formula (1) in the presence of a base compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29116789A JP2933955B2 (en) | 1989-11-10 | 1989-11-10 | Purification method of chroman compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29116789A JP2933955B2 (en) | 1989-11-10 | 1989-11-10 | Purification method of chroman compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03153678A JPH03153678A (en) | 1991-07-01 |
| JP2933955B2 true JP2933955B2 (en) | 1999-08-16 |
Family
ID=17765315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29116789A Expired - Lifetime JP2933955B2 (en) | 1989-11-10 | 1989-11-10 | Purification method of chroman compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2933955B2 (en) |
-
1989
- 1989-11-10 JP JP29116789A patent/JP2933955B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03153678A (en) | 1991-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| HU198437B (en) | Process for producing mono- or bis-carbonyl-compounds | |
| EP0621861A1 (en) | A method of preparing carboxylic acids or esters thereof by the oxidative cleavage of unsaturated fatty acids or esters thereof. | |
| EP0257619A2 (en) | Process for preparing 3-halogeno-2-hydroxypropyltrimethylammonium halide | |
| JP2933955B2 (en) | Purification method of chroman compounds | |
| JP2830210B2 (en) | Synthesis of α, β-unsaturated ketones | |
| EP1174413B1 (en) | Process for production of carboxylic acid aryl esters | |
| JP3285391B2 (en) | Method for producing 2-phenoxybenzoic acid | |
| US4496771A (en) | Process for preparing the compound 1-decyloxy-4-[(7-oxa-4-octynyl)-oxy]-benzene | |
| JP2005511777A (en) | Production of trimethylhydroquinone diacylate | |
| JP3252491B2 (en) | Binaphthol derivative and method for producing the same | |
| JP2502936B2 (en) | Novel acetylene derivative | |
| EP0600714A1 (en) | Process for producing O,O'-diacyltartaric anhydride and process for producing O,O'-diacyltartaric acid | |
| JPH0710813A (en) | Optical resolution of alpha-phenetylamine compound | |
| EP0118257A1 (en) | Optical resolution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyldioxide | |
| EP0194849A2 (en) | Improved process for producing N-acyl-acyloxy aromatic amines | |
| EP1318132A1 (en) | Process for producing 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane | |
| JP2640688B2 (en) | Carbamate derivatives and methods for their production | |
| JP3569428B2 (en) | Method for producing homoallylamines | |
| EP0318591B1 (en) | Process for preparing dihydroxynaphthalene | |
| SU1567565A1 (en) | Method of obtaining 1-chlor-4-methylpentan 2-ol | |
| EP1403238A1 (en) | Process for producing fluorinated alcohol | |
| JPH0344349A (en) | Production of p-or m-hydroxybenzaldehyde | |
| JP4073344B2 (en) | Method for producing methyltrifluoromethylbenzoic acid | |
| JPH0741452A (en) | Production of 4-(3-oxoalkyl)phenol | |
| JPH0687779A (en) | Production of iodinated benzene derivative |