KR920009557B1 - Method for stabilizing o,o-dimethyl dithiophosphoryl phenylacetic acid - Google Patents
Method for stabilizing o,o-dimethyl dithiophosphoryl phenylacetic acid Download PDFInfo
- Publication number
- KR920009557B1 KR920009557B1 KR1019850001140A KR850001140A KR920009557B1 KR 920009557 B1 KR920009557 B1 KR 920009557B1 KR 1019850001140 A KR1019850001140 A KR 1019850001140A KR 850001140 A KR850001140 A KR 850001140A KR 920009557 B1 KR920009557 B1 KR 920009557B1
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- present
- stabilizing
- dithiophosphoryl
- dimethyl
- Prior art date
Links
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
Abstract
내용 없음.No content.
Description
본 발명은 하기 구조식 (I)의 o,o-디메틸디티오포스포릴페닐 아세트산 2몰에 대하여, 하기 일반식(II)의 화합물 또는 사이클로헥센으로부터 선택된 화합물(이하 간단히 ＂첨가제＂라 한다. 1종 또는 2종 이상을 총 1몰 이상의 양으로 첨가함을 특징으로 하여 구조식(I)의 o,o-디메틸디티오포스포릴페닐 아세트산을 안정화시키는 방법에 관한 것이다.The present invention refers to a compound selected from a compound of the following general formula (II) or cyclohexene with respect to 2 moles of o, o-dimethyldithiophosphorylphenyl acetic acid of the following structural formula (I) (hereinafter simply referred to as “additive”). Or stabilizing o, o-dimethyldithiophosphorylphenyl acetic acid of formula (I), characterized in that at least two species are added in an amount of at least 1 mole in total.
상기식에서, X는 수소원자, 메틸그룹 또는 할로겐원자를 나타낸다.Wherein X represents a hydrogen atom, a methyl group or a halogen atom.
농업용 살충제로서 시판되고 있는 PAP제(일반명)의 유효성분 화합물의 중간체로 알려져 있는 본 발명의 구조식(I)의 o,o-디메틸디티오포스포릴페닐 아세트산은 다음 반응도식에 따라 제조된다.The o, o-dimethyldithiophosphorylphenyl acetic acid of Structural Formula (I) of the present invention known as an intermediate of an active ingredient compound of a commercially available PAP agent (common name) as an agricultural pesticide is prepared according to the following scheme.
본 발명의 화합물(I)이 상기 반응도식(I)에 따라 제조되고, 이후에 상기 반응도식(2)에 따라 목적 화합물(III)이 제조되고 있지만, 중간체인 본 발명의 화합물(I)은 화학적으로 불안정하기 때문에 시간이 경과함에 따라 변화가 현저하고, 이로 인해 순도가 저하되어 목적 화합물(I)의 수율이 저하되며, 따라서 장기간의 저장 및 수송에 부적합하고, 특히 고온인 경우 시간이 경과에 따른 변화가 현저히 커지는 결점을 갖고있다.,Compound (I) of the present invention is prepared according to Scheme (I), and then Compound (I) of the present invention, which is an intermediate, is prepared according to Scheme (2). Because of its instability, the change is remarkable with time, resulting in lower purity and lower yield of the target compound (I), and thus unsuitable for long-term storage and transport, especially at high temperatures. It has the drawback that the change is significant.
본 발명의 화합물(I)을 안정화시키는 방법으로서 포름산 및/또는 옥산살을 첨가하는 방법이 공지되어 있다[참조 :일본국 공개특허공보 제 (소) 55-130989호]. 그러나, 포름산 등을 첨가하는 방법은, 포름산 등이 갖는 금속부식성 때문에 내부식성이 있는 특별한 용기에 저장하여야 하고, 또한 포름산 등이 첨가된 본 발명의 화합물(I)을 상기 반응도식(2)의 반응에 사용하기 위해서는 첨가된 포름산 등을 제거하는 공정이 필요하다는 결점이 있다.As a method of stabilizing the compound (I) of the present invention, a method of adding formic acid and / or oxalate is known (see Japanese Patent Laid-Open No. 55-130989). However, the method of adding formic acid or the like should be stored in a special container having corrosion resistance due to the metal corrosion resistance of formic acid and the like. The drawback is that a process for removing added formic acid or the like is necessary for use.
본 발명은, 포름산 등을 첨가하여 본 발명의 화합물(I)을 안정화시키는 방법과는 전혀 그 기술적 사상이 다르다 .The present invention is completely different from the technical idea of the method of stabilizing the compound (I) of the present invention by adding formic acid or the like.
본 발명은 액상의 본 발명의 혼합물(I) 2몰에 대하여, 액상의 일반식(II)의 화합물 또는 사이클로헥센으로부터 선택되는 화합물 1종 또는 2종 이상으로 이루어진 화합물을 약 1몰 이상 첨가함으로써 고체결정인 분자화합물을 생성시키는 것이다. 즉 상온에서 액체상태인 화합물들을 분자 화합물로 변화시켜, 분자 운동이 억제된 고체 결정으로 되게 함으로써, 본 발명의 화합물(I)의 화학적 안정화를 달성할 수 있음을 발견한것이다.The present invention provides a solid by adding about 1 mole or more of a compound selected from the compound of general formula (II) or cyclohexene in a liquid phase to 2 moles of the mixture (I) in the liquid phase. To produce molecular compounds that are crystals. In other words, it was found that chemical stabilization of the compound (I) of the present invention can be achieved by changing the compounds in the liquid state at room temperature into molecular compounds, thereby making the solid crystals with reduced molecular motion.
본 발명의 화합물(I)과 첨가제로부터 생성되는 분자 화합물(고체 결정)은 그 형태 그대로 상기 반응도식(2)의 반응에 사용될 수 있고, 또한 첨가제는 반응에 전혀 악영향을 미치지 않으며 반응용매의 하나로서 사용될 수 있다.The molecular compound (solid crystal) produced from the compound (I) and the additive of the present invention can be used in the form of the reaction scheme (2) as it is, and the additive does not adversely affect the reaction at all and is one of the reaction solvents. Can be used.
본 발명에 있어서의 첨가제로서는, 예를 들면, 벤젠, 톨루엔, 클로로벤젠, 브로모 벤젠, 요오드 벤젠, 플루오로 벤젠 및 사이클로 헥센 등이 있다.Examples of the additive in the present invention include benzene, toluene, chlorobenzene, bromo benzene, iodine benzene, fluorobenzene, cyclohexene, and the like.
첨가제의 첨가량으로서는, 본 발명의 화합물(I) 2몰에 대하여, 첨가제가 약 1몰 이상 필요하며, 첨가량이 1몰 이하이면 충분한 분자 화합물(고체 결정)을 수득하기 어렵고, 그 결과 본 발명의 화합물(I)의 분해를 억제하기가 어려워지고, 충분히 안정화되지 못한다.As addition amount of an additive, about 1 mol or more of additives are necessary with respect to 2 mol of compound (I) of this invention, and when the addition amount is 1 mol or less, sufficient molecular compound (solid crystal) is difficult to be obtained, As a result, the compound of this invention It becomes difficult to suppress decomposition of (I) and it does not stabilize sufficiently.
하기에 본 발명의 실시예를 구체적으로 상세히 설명하지만, 본 발명이 이에 한정되지는 않는다,Examples of the present invention will be described in detail below, but the present invention is not limited thereto.
실시예Example
o,o-디메틸디티오포스포릴페닐 아세트산 2몰에 대하여, 하기 표 1에 기재된 첨가제를 0.5내지 1.5몰 첨가하여, 각각 시험 샘플로 한다. 또한 비교 첨가제로서 크실렌 및 메탄올을 시험 샘플로 한다. 이들 시험샘플을 각각 두껑이 있는 유리 샘플병에 넣고 40℃에서 3개월 동안 학대시험을 한다.To 2 moles of o, o-dimethyldithiophosphorylphenyl acetic acid, 0.5 to 1.5 moles of the additives shown in Table 1 below were added to prepare test samples. In addition, xylene and methanol are used as test samples as comparative additives. Each of these test samples is placed in a glass sample bottle with a lid and subjected to abuse for 3 months at 40 ° C.
시험후 고속 액체 크로마토그래피(내부표준법)로 o, o-디메틸디티오포스포릴페닐 아세트산 [본 발명의 화합물()]의 순도를 측정하여 각각의 분해율을 측정한다.After the test, the decomposition rate is measured by measuring the purity of o, o-dimethyldithiophosphorylphenylacetic acid [compound () of the present invention] by high performance liquid chromatography (internal standard method).
결과를 표 1에 기재한다.The results are shown in Table 1.
[표 1]TABLE 1
표 1로부터 명백한 바와 같이, 첨가제가 없는 경우에 본 발명의 화합물(I)이 77.6% 분해된 것에 비하여 , 본 발명의 첨가제를 1몰 이상 첨가한 것은 분해가 1% 전후로 억제된다. 그러나, 첨가제가 존재하여도 이의 첨가량이 0.5몰인 경우에는 분해가 억제되지 않는다. 또한, 본 발명에 규정한 첨가제 이외의 크실렌 및 메탄올은 첨가량이 1몰 이상인 경우에도 분해를 억제할 수 없다.As is apparent from Table 1, in the absence of an additive, the compound (I) of the present invention was decomposed by 77.6%, whereas the addition of one or more moles of the additive of the present invention was suppressed around 1%. However, even if an additive is present, decomposition is not suppressed when the amount thereof is 0.5 mol. In addition, xylene and methanol other than the additive prescribed | regulated by this invention cannot suppress decomposition, even if addition amount is 1 mol or more.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59034785A JPS60178895A (en) | 1984-02-24 | 1984-02-24 | Method for stabilizing o,o-dimethyl dithiophosphorylphenylacetic acid |
| JP59-34785 | 1984-02-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR850007064A KR850007064A (en) | 1985-10-30 |
| KR920009557B1 true KR920009557B1 (en) | 1992-10-19 |
Family
ID=12423928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019850001140A KR920009557B1 (en) | 1984-02-24 | 1985-02-23 | Method for stabilizing o,o-dimethyl dithiophosphoryl phenylacetic acid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS60178895A (en) |
| KR (1) | KR920009557B1 (en) |
-
1984
- 1984-02-24 JP JP59034785A patent/JPS60178895A/en active Granted
-
1985
- 1985-02-23 KR KR1019850001140A patent/KR920009557B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0410476B2 (en) | 1992-02-25 |
| JPS60178895A (en) | 1985-09-12 |
| KR850007064A (en) | 1985-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gawne et al. | Acyloxyphosphonium salts as acylating agents. Synthesis of peptides | |
| US5175353A (en) | 2-(2'-aminoethoxy)-ethanol salt of dicamba | |
| IE791565L (en) | Crop cutting apparatus | |
| KR920009557B1 (en) | Method for stabilizing o,o-dimethyl dithiophosphoryl phenylacetic acid | |
| JP4278205B2 (en) | Compositions of aliphatic alkanals and methods for improving the storage stability of the compounds | |
| Boersma et al. | A new, easy synthesis of phenylsilver | |
| GB1496469A (en) | N-(1,2,4-triazin-5-on-4-yl)-glycine derivatives process for their preparation and their use as herbicides | |
| US2786078A (en) | Stabilization of methylenedinitramine | |
| KR830010083A (en) | Method for preparing substituted acetanilide derivatives | |
| US2965538A (en) | Biological toxicants | |
| GB973920A (en) | Sulphenic acid derivatives | |
| US4478755A (en) | Titanate compositions having depressed freezing points | |
| Gunther | Dichlorodiphenyltrichloroethane. I. Solubility in various solvents | |
| US2909543A (en) | Complexes of sulfonium compounds | |
| JPS595575B2 (en) | Hydroxylamine stabilizer | |
| Lo et al. | 5-Alkoxymethylenerhodanines and their Reactions with Rhodanines1 | |
| ES444521A1 (en) | Biocidal uses of pyridyltriazinone compounds | |
| US3998854A (en) | Trithiophosphite stabilized maleic anhydride | |
| US4010185A (en) | Stable oil-soluble metal sulfonate analytical standards | |
| DeMember et al. | Silver (I) chemistry in aqueous alkaline media. 2. Study of the interaction of silver (I) with. beta.-disulfone carbanions in aqueous alkaline media | |
| US2329883A (en) | Mercuri-acetylide compound and method of preparing the same | |
| KR830009030A (en) | Method for preparing phenoxy pyridyl methyl ester | |
| US3959323A (en) | Oil soluble mercury compound for an analytical standard | |
| US3305588A (en) | Alpha-acylvinylthioethers | |
| EP0227913B1 (en) | Stabilized gossyplure and methods for preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| G160 | Decision to publish patent application | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20001011 Year of fee payment: 9 |
|
| LAPS | Lapse due to unpaid annual fee |