KR950004178B1 - Method of preparing o-ethyl-s,s-dipropye phosphorodithioate - Google Patents
Method of preparing o-ethyl-s,s-dipropye phosphorodithioate Download PDFInfo
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- KR950004178B1 KR950004178B1 KR1019920012544A KR920012544A KR950004178B1 KR 950004178 B1 KR950004178 B1 KR 950004178B1 KR 1019920012544 A KR1019920012544 A KR 1019920012544A KR 920012544 A KR920012544 A KR 920012544A KR 950004178 B1 KR950004178 B1 KR 950004178B1
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- Prior art keywords
- ethyl
- normal propyl
- propyl mercaptan
- salt
- dipropylphosphorodithioate
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- 238000000034 method Methods 0.000 title claims description 15
- NAGJZTKCGNOGPW-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [O-]P([O-])([S-])=S NAGJZTKCGNOGPW-UHFFFAOYSA-K 0.000 title 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims abstract description 80
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 8
- VJYFKVYYMZPMAB-UHFFFAOYSA-N ethoprophos Chemical compound CCCSP(=O)(OCC)SCCC VJYFKVYYMZPMAB-UHFFFAOYSA-N 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 2
- HJHVQCXHVMGZNC-JCJNLNMISA-M sodium;(2z)-2-[(3r,4s,5s,8s,9s,10s,11r,13r,14s,16s)-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12,13,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-ylidene]-6-methylhept-5-enoate Chemical compound [Na+].O[C@@H]([C@@H]12)C[C@H]3\C(=C(/CCC=C(C)C)C([O-])=O)[C@@H](OC(C)=O)C[C@]3(C)[C@@]2(C)CC[C@@H]2[C@]1(C)CC[C@@H](O)[C@H]2C HJHVQCXHVMGZNC-JCJNLNMISA-M 0.000 claims 2
- 239000002917 insecticide Substances 0.000 abstract description 2
- 239000005645 nematicide Substances 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000005626 carbonium group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- -1 O-ethyl phospho dichlorate Chemical compound 0.000 description 1
- 241001465382 Physalis alkekengi Species 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- LAFREWHFZMQREH-UHFFFAOYSA-N hydroxy-propoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCOP(O)(S)=S LAFREWHFZMQREH-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
Description
[발명의 명칭][Name of invention]
O-에틸-S, S-디프로필 포스포로디티오에이트의 제조방법Method for preparing O-ethyl-S, S-dipropyl phosphorodithioate
[발명의 상셰한 설명][Simple explanation of invention]
본 발명은 유기인계 농약인 O-에틸-S, S-디프로필 포스포로디티오에이트의 제조방법에 관한 것이다.The present invention relates to a process for producing O-ethyl-S and S-dipropyl phosphorodithioate which are organophosphorus pesticides.
일반적으로 상기 화합물은 벼의 심고선층, 흰등멸구, 벼멸구 및 감자 거세미나방의 방제에 사용되는 살선충, 살충제의 중간체로서 유용한 것으로 널리 알려져 있으며, 이를 제조하는 대표적인 방법들로서는 미합중국 특허 제3,268,393호(이하, '393 특허라 함) 및 네덜란드 특허 제6,608,632호(이하 '632 특허라 함)가 있다.In general, the compound is widely known to be useful as an intermediate of nematicides and insecticides used in the control of rice seedlings, white lanterns, rice bran and potato castor moths of rice. Representative methods for preparing the same include US Pat. No. 3,268,393 , The '393 patent) and Dutch Patent No. 6,608,632 (hereinafter referred to as the' 632 patent).
상기 '393 특허에서는 노르말프로필메르캅탄과 포스포로트리클로라이드를 반응시켜서 S, S-디프로필포스포로클로리도디티오이티이를 합성하고, 이것을 헥산 용제하에서 에틸알콜, 트리에틸아민과 반응시켜서 O-에틸-S, S-디프로필포스포로디티오이티이를 합성하고 이를 다시 과산화수소와 반응시켜서 상기 목적화합물을 제조하였다.In the '393 patent, S, S-dipropylphosphorochloridodithiothiyi is synthesized by reacting normal propylmercaptan with phosphorotrichloride, which is reacted with ethyl alcohol and triethylamine in hexane solvent to give O-ethyl. -S, S-dipropylphosphorodithioti was synthesized and reacted with hydrogen peroxide to prepare the target compound.
상기 '632 특허에서는 포스포로스옥시클로라이드와 에틸알콜을 반응시켜서 O-에틸포스포로스디클로리데이트를 합성하고, 노르말프로필메르캅탄과 산담체를 반응시켜서 노르말프로필메르캅탄염을 합성한다. 그 다음에 O-에틸 포스포로디클로리데이트와 노르말프로필메르캅탄염을 불활성의 유기용제하에서 격렬하게 교반시켜서 상기 목적화합물을 제조하였다.In the '632 patent, O-ethylphosphorose dichlorate is synthesized by reacting phosphorus oxychloride with ethyl alcohol, and normal propyl mercaptan salt is synthesized by reacting normal propyl mercaptan with an acid carrier. Then, O-ethyl phosphorodichlorate and normal propylmercaptan salt were vigorously stirred under an inert organic solvent to prepare the target compound.
그러나, 상기 '393 특허에서는 노르말프로필메르캅탄과 포스포로스트리클로라이드를 반응시킨 후 5mmHg의 진공도와 140℃ 이상의 고온하에서 분별증류를 해야하고, O-에틸-S, S-디프로필포스포로디티이이티이를 합성한 후에는 부반응으로 생성된 트리에틸아민하이드로클로라이드를 제거하기 위해 여과해야 하며, 용매로 사용된 헥산을 제거하기 위해 분별증류를 실시해야 하고, 또 벤젠 리플럭스하에 O-에틸-S, S-디프로필포스포로디티오이티이를 과산화수소로 산화시켜서 O-에틸-S, S-디프로필포스포로디티오에이트를 합성하고, 미반응 과산화수소를 제거하기 위해 5% 가성소다액으로 세척하고, 헥산을 제거하기 위해 30mmHg의 진공도와 100℃의 고온에서 증류를 실시해야만 한다. 상술한 바와같이, 상기 '393 특허에서는 고진공, 고온하에서 여러번의 분별증류를 실시해야 하므로 공정이 복잡하고, 특히 트리에틸아민과 같은 반응성이 낮은 알칼리를 산성담체로 사용하기 때문에 수율이 매우 낮다. 또한 반응중 부반응이 많아 순도가 낮고, 값비싼 트리에틸아민과 과산화수소를 사용하므로 공업적으로 적합하지 못한 문제점이 있었다.However, in the '393 patent, after reacting normal propylmercaptan and phosphorotrichloride, fractional distillation is performed under a vacuum of 5 mmHg and a high temperature of 140 ° C or higher, and O-ethyl-S and S-dipropylphosphorodithiyi After the synthesis, it is necessary to filter to remove triethylamine hydrochloride produced by side reaction, fractional distillation to remove hexane used as solvent, and O-ethyl-S, S- under benzene reflux. Di-propylphosphorodithioti is oxidized with hydrogen peroxide to synthesize O-ethyl-S, S-dipropylphosphorodithioate, washed with 5% caustic soda solution to remove unreacted hydrogen peroxide, and hexane removed. To do this, distillation should be performed at a vacuum of 30 mmHg and at a high temperature of 100 ° C. As described above, the '393 patent requires a number of fractional distillations under high vacuum and high temperature, and thus the process is complicated. In particular, the yield is very low because the low reactivity alkali such as triethylamine is used as the acid carrier. In addition, there are many side reactions during the reaction, the purity is low, and expensive triethylamine and hydrogen peroxide are used, there is a problem that is not industrially suitable.
상기 '632 특허에서는 O-에틸포스포로디클로리데이트와 노르말프로필메르캅탄염을 다량의 불활성 유기용제하에서 반응시키므로 용제 사용량 만큼 생산용량이 작아지고, 또한 노르말프로필메르캅탄염은 수용성이므로 교반이 어렵고, 용제회수공정이 필요한 단점이 있고, 또 산성담체로서 소디움금속, 포타시음하이드록사이드플레이크, 트리에틸아민을 사용하는데, 트리에틸아민을 사용하는 공정은 수율이 매우 낮고, 소디움금속을 사용하는 공정은 수소가 다량 발생하여 이의 처리 및 안전에 문제가 있고, 포타시움하이드록사이드는 값이 비싼 문제점이 있다.In the '632 patent, since O-ethylphosphorodichlorate and the normal propyl mercaptan salt are reacted under a large amount of inert organic solvent, the production capacity is reduced by the amount of solvent used, and since the normal propyl mercaptan salt is water-soluble, it is difficult to stir. In addition, there is a disadvantage in that a solvent recovery process is required, and as an acid carrier, sodium metal, potassium hydroxide flakes, and triethylamine are used. The process using triethylamine has a very low yield and a process using sodium metal. A large amount of hydrogen is generated, there is a problem in its treatment and safety, and potassium hydroxide has a problem that is expensive.
또한, 상기 '632 특허에서는 세척시에 물과의 분액이 명확히 되게 하기 위하여 비중이 낮은 유기용제를 반응용매로 사용하였고, 반응중간체 및 O-에틸-S, S-디프로필포스포로디티오에이트가 물과 알카리에 약하다고 알려져 있으므로 근본적으로 물이 배제된, 유기용제하에서 반응을 진행시켰다. 그러나, 노르말프로필메르캅탄염은 수용성으로서 유기용제하에서는 교반상의 어려움이 있었고, O-에틸포스포로디클로라이드와 노르말프로필메르캅탄염을 당량 대 당량으로 반응시켰기 때문에 반응도중 O-에틸포스포로디클로리데이트가 상당량 분해되어서 수율이 낮은 문제점이 있다.In addition, in the '632 patent, an organic solvent having a low specific gravity was used as a reaction solvent in order to clarify the separation with water during washing, and the reaction intermediate and O-ethyl-S and S-dipropylphosphorodithioate were used. It is known to be weak to water and alkali, so the reaction proceeds under organic solvent, which is essentially free of water. However, normal propyl mercaptan salts were water-soluble and had difficulty in stirring under organic solvents, and O-ethyl phosphoro dichloride during the reaction was performed because O-ethylphosphorodichloride and normal propyl mercaptan salts were reacted in an equivalent to equivalent amount. There is a problem that the yield is low because the date is decomposed significantly.
이러한 문제점을 해결하기 위하여 본 발명자들은 광범위한 연구를 수행한 결과, 물 존재하에서 노르말프로필메르캅탄염과 O-에틸포스포로디티오에이트를 반응시키면 수용성인 노르말프로필메르캅탄염 이 완전히 용해되어 교반이 어려운 문제점을 해결할 수 있다는 점을 발견하였고 본 발명은 상기 발견에 기초하여 완성되었다.In order to solve this problem, the present inventors conducted extensive research, and when the normal propylmercaptan salt reacts with O-ethylphosphorodithioate in the presence of water, the water-soluble normal propylmercaptan salt is completely dissolved, making it difficult to stir. It has been found that the problem can be solved and the present invention has been completed based on the above finding.
따라서, 본 발명의 목적은 물 존재하에서 노르말프로필메르캅탄염과 O-에틸포스포로디클로리데이트를 반응시켜 O-에틸-S, S-디프로필포스포로디티오에이트를 제조하는 방법을 제공하는데 있다.Accordingly, an object of the present invention is to provide a method for preparing O-ethyl-S, S-dipropylphosphorodithioate by reacting normal propylmercaptan salt with O-ethylphosphorodichlorate in the presence of water. have.
본 발명의 다른 목적은 극성용매 또는 물과 극성용매의 혼합용매하에서 노르말프로필메르캅탄염과 O-에틸포스포로디클로리데이트를 반응시켜 O-에틸-S, S-디프로필포스포로디티오에이트를 제조하는 방법을 제공하는데 있다.Another object of the present invention is to react O-ethyl-S, S-dipropylphosphorodithioate by reacting normal propylmercaptan salt with O-ethylphosphorodichlorate in a polar solvent or a mixed solvent of water and polar solvent. To provide a method for producing a.
상기 목적을 달성하고자 본원 발명의 제조방법은 산성담체로서 알칼리 수용액을 사용하고, 노르말프로필메르캅탄을 알칼리 수용액보다 과량으로 사용하여 노르말프로필메르캅탄염을 합성하고, 노르말프로필메르캅단염과 O-에틸포스포로디클로리데이트를 물 존재하에서 반응시킨 후 미반응 노르말프로필메르캅탄염은 산과 반응시켜 노르말프로필메르캅탄으로 회수하는 것으로 구성된다.In order to achieve the above object, the preparation method of the present invention uses an aqueous alkaline solution as an acid carrier, synthesizes a normal propyl mercaptan salt using an excess amount of normal propyl mercaptan than an aqueous alkaline solution, and prepares a normal propyl mercapdan salt and O-ethyl. After reacting phosphorodichlorate in the presence of water, the unreacted normalpropylmercaptan salt consists of reacting with acid to recover to normalpropylmercaptan.
이하 본 발명의 제조방법을 좀 더 구체적으로 살펴보면 다음과 같다.Looking in more detail below the manufacturing method of the present invention.
먼저, 노르말프로필메르캅탄에 알칼리 수용액을 적하하면서 동시에 교반하여 노르말프로필메르캅탄염을 제조한다. 이때 사용되는 알칼리 소디움하이드록사이드, 포타시움 하이드록사이드 또는 암모니움하이드록사이드가 바람직하다. 상기 노르말프로필메르캅탄의 량은 알칼리 수용액보다 10∼200%과량이 바람직한데, 이는 미반응 알카리가 적도록하여 알카리에 약한 O-에틸포스포로디클로리데이트와 O-에틸-S, S-디프로필포스포로디티오에이트가 분해되는 것을 방지하고, 과량으로 사용된 노르말프로필메르캅탄이 용제의 역할을 수행하기 때문이다.First, an aqueous alkali solution is added dropwise to normal propyl mercaptan while stirring to prepare a normal propyl mercaptan salt. Alkali sodium hydroxide, potassium hydroxide or ammonium hydroxide used at this time is preferable. The amount of the normal propyl mercaptan is preferably 10 to 200% over the aqueous alkali solution, which is less reactive alkali, O-ethylphosphorodichlorate and O-ethyl-S, S-di This is because propylphosphorodithioate is prevented from being degraded and normal propylmercaptan used in excess serves as a solvent.
그 다음 상기 노로말프로필메르캅탄염에 O-에틸포스포로디클로리데이트를 서서히 적하하는데, 이때의 반응온도는 -20℃에서 반응물의 끓는점까지 가능하나 0∼50℃ 범위가 바람직하다. 상기 -20℃ 이하에서는 동력비가 과다하게 소요되므로 상업적으로 적합하지 않고, 상기 끓는점을 초과하면 O-에틸포스포로디클로리데이트가 급격히 분해되는 문제점이 있다.Then, O-ethylphosphorodichloridate is slowly added dropwise to the normal propylmercaptan salt. At this time, the reaction temperature is preferably from -20 ° C to the boiling point of the reactant, but is preferably in the range of 0 to 50 ° C. Since the power ratio is excessively below -20 ° C., it is not commercially suitable, and when the boiling point is exceeded, O-ethylphosphorodichlorate rapidly decomposes.
또한, 본 발명은 물 존재하에서 노로말프로필메르캅탄염을 O-에틸포스포로디클로리데이트 당량보다 과량을 반응시키고, 미반응 노르말프로필메르캅탄염은 산과 반응시켜 노르말프로필메르캅탄으로 회수하는 것으로 구성된다.In addition, the present invention is to react the excess of the normal propyl mercaptan salt in the presence of water than the equivalent of O-ethylphosphorodichlorate, and to recover the unreacted normal propyl mercaptan salt with acid to recover the normal propyl mercaptan It is composed.
상기 노르말프로필메르캅탄염의 량은 O-에틸포스포로디클로리데이트 당량보다 10∼300%과량이 바람직한데, 상기 범위를 초과하면 생산량이 적어지는 문제점이 있다. 상기 반응에 사용되고 남은 과량의 노르말프로필메르캅탄염은 10∼80% 질산, 황산, 초산 또는 염산과 반응시켜 노르말프로필메르캅탄으로 제조한 다음, 증류하여 회수하는 것이 바람직하다.The amount of the normal propyl mercaptan salt is preferably 10-300% excess than the O-ethylphosphorodichloride equivalent, there is a problem that the production amount is less than the above range. Excess normal propyl mercaptan salt used in the reaction is preferably prepared by reacting with 10 to 80% nitric acid, sulfuric acid, acetic acid or hydrochloric acid to make normal propyl mercaptan, and then distilled to recover.
본 발명의 다른 목적을 달성하기 위하여 본 발명은 극성용매 또는 극성용매와 물과의 혼합용매하에서 노르말프로필메르캅탄을 알칼리 수용액보다 과량으로 사용하여 노르말프로필메르캅탄염을 합성하고, 상기 노르말프로필메르캅단염과 O-에틸포스포로디클로리데이트를 반응시킨후 물을 넣고 교반후 용매를 회수하는 것으로 구성된다.In order to achieve another object of the present invention, the present invention synthesizes a normal propyl mercaptan salt using an excess amount of normal propyl mercaptan than an aqueous alkali solution in a polar solvent or a mixed solvent of polar solvent and water, and the normal propyl mercap The reaction consists of recovering the solvent after stirring with water and adding O-ethylphosphorodichlorate.
상기 극성용매로는 1,4-디옥산, 테트라하이드로퓨란 또는 디메틸설퍼옥사이드등이 사용되나, 이에 한정되는 것은 아니며, 이들과 물의 혼합비율은 7 : 1∼9.5 : 0.5이 바람직하다. 상기 혼합비는 수용성인 노르말프로필메르캅탄염이 혼합용매에 적절히 용해되기에 적합한 비율이다.As the polar solvent, 1,4-dioxane, tetrahydrofuran, or dimethyl sulfoxide may be used, but is not limited thereto. The mixing ratio of these and water is preferably 7: 1 to 9.5: 0.5. The said mixing ratio is a ratio suitable for melt | dissolving the water-soluble normal propyl mercaptan salt suitably in a mixed solvent.
상기 제조방법에 사용되는 알칼리로는 소디움하이드록사이드, 포타시움하이드록사이드 또는 암모니움하이드록사이드가 바람직하고, 노르말프로필메르캅탄의 량은 알칼리 수용액보다 10∼200%과량이 바람직하다.As an alkali used for the said manufacturing method, sodium hydroxide, a potassium hydroxide, or an ammonium hydroxide is preferable, and the quantity of normal propyl mercaptan is 10-200% more preferable than aqueous alkali solution.
상기 노르말프로필메르캅단염에 O-에틸포스포로디클로리데이트를 반응시키는 온도 또한 -20℃에서 반응물의 끓는점까지 가능하나 0∼50℃ 범위가 바람직하다.The temperature at which O-ethylphosphorodichlorate reacts with the normal propylmercaptan salt is also possible from -20 ° C to the boiling point of the reactant, but is preferably in the range of 0 to 50 ° C.
상기 반응은 주로 상압 또는 가압하에서 진행되며, 가압은 반응기 내에 잔류하는 산소로 인한 산화를 방지하기 위하여 일시적으로 또는 지속적으로 유입시키는 불활성 기체에 의해 이루어진다. 사용가능한 불활성기체는 헬륨, 아르곤, 질소등이 바람직하고 사용압력은 상압에서 10kg/cm2가 바람직하다.The reaction proceeds mainly at atmospheric pressure or under pressure, and the pressurization is carried out by an inert gas which is introduced temporarily or continuously in order to prevent oxidation due to oxygen remaining in the reactor. The inert gas that can be used is preferably helium, argon, nitrogen and the like, and the working pressure is preferably 10 kg / cm 2 at atmospheric pressure.
이하, 실시예를 통해 본 발명의 제조방법 및 그 효과에 대해서 구체적으로 설명하지만, 하기 예들이 본발명의 범주를 한정하는 것은 아니다.Hereinafter, the production method and effects of the present invention will be described in detail with reference to Examples, but the following examples do not limit the scope of the present invention.
(실시예 1)(Example 1)
노르말프로필메르캅탄 1.3몰(99g)을 반응기에 넣고, 10℃에서 20% 소디움하이드록사이드 수용액 1몰(200g)을 1시간동안 교반하면서 적하하여 노르말프로필메르캅탄소디움염을 합성했다. 여기에 O-에틸포스포로디클로리데이트 0.294몰(47.8g)을 10℃에서 교반하면서 1시간 동안 서서히 적하했다. 10℃에서 30분동안 교반하여 반응을 완결시킨다음, 35% 염산을 교반하면서 투입하여 pH 2∼3으로 조절하고, 물로 2회 세척했다. 유기층은 진공증류하여 과량의 노르말프로필메르캅탄 20g을 희수하고 가스크로마토그라피에 의한 순도 94.5%, 수득율 88.2%이었다.1.3 mol (99 g) of normal propyl mercaptan was placed in a reactor, and 1 mol (200 g) of a 20% sodium hydroxide aqueous solution was added dropwise at 10 DEG C while stirring for 1 hour to synthesize normal propyl mercap carbonium salt. 0.294 mol (47.8 g) of O-ethylphosphorodichlorate was slowly dripped at this for 1 hour, stirring at 10 degreeC. The reaction was completed by stirring at 10 ° C. for 30 minutes, and then 35% hydrochloric acid was added while stirring to adjust the pH to 2-3 and washed twice with water. The organic layer was distilled under vacuum to dilute an excess of 20 g of normal propylmercaptan, and the purity was 94.5% by gas chromatography and the yield was 88.2%.
(실시예 2)(Example 2)
노르말프로필메르캅탄 2몰(152.3g)을 반응기에 넣고, 10℃에서 20% 소디움하이드록사이드 수용액 2몰(400g)을 1시간반동안 교반하면서 적하하여 노르말프로필메르캅탄소디움염을 합성했다. 여기에 O-에틸포스포로디클로리데이트 0.5몰(81.3g)을 10℃에서 교반하면서 2시간 동안 서서히 적하했다. 10℃ 미만에서 30분동안 교반하여 반응을 완결시켰다. 이후의 공정은 실시예 1과 동일하며 연노랑색의 O-에틸-S, S-디프로필포스포로에이트 127.4g을 얻었다. 가스크로마토그라피에 의한 순도 95.1% 수득율 84.2%이었다.2 mol (152.3 g) of normal propyl mercaptan was placed in a reactor, and 2 mol (400 g) of 20% sodium hydroxide aqueous solution was added dropwise while stirring at 10 DEG C for 1 hour and half to synthesize normal propyl mercap carbonium salt. 0.5 mol (81.3 g) of O-ethylphosphorodichlorate was slowly added dropwise thereto over 2 hours with stirring at 10 占 폚. The reaction was completed by stirring at less than 10 ° C. for 30 minutes. The subsequent process was the same as that of Example 1, and 127.4 g of light yellow O-ethyl-S and S-dipropylphosphorate were obtained. Purity 95.1% yield 84.2% by gas chromatography.
(실시예 3)(Example 3)
노르말프로필메르캅탄 1물(76.2g)을 1,4-디옥산/물(90 : 10) 혼합용매 270m1에 넣고 30℃ 이하에서 45% 소디움하이드록사이드 수용액 1몰(88.9g)을 1시간동안 교반하면서 적하하여 노르말프로필메르캅탄소디움염을 합성했다. 이 반응혼합물에 O-에틸포스포로디클로리데이트 0.5몰(81.3g)을 10℃에서 교반하면서 2시간동안 서서히 적하했다. 10℃에서 30분동안 교반하여 반응을 완결시키고, 물 116g을 넣고 30분간 교반했다. 유기층을 분리한 후 진공증류하여 1,4-디옥산을 회수하고, 잔류물로 연노랑색의 O-에틸-S, S-디프로필포스포로디티오에이트 96.4g을 얻었다. 가스크로마토그라피에 의한 순도 98%, 수득율 76%이었다.1 mol (76.2 g) of normal propyl mercaptan was added to 270 m 1 of a 1,4-dioxane / water (90:10) mixed solvent, and 1 mol (88.9 g) of 45% sodium hydroxide solution at 30 ° C. or lower for 1 hour. It dripped stirring, and the normal propyl mercap carbonium salt was synthesize | combined. 0.5 mol (81.3 g) of O-ethylphosphorodichlorate was slowly added dropwise to the reaction mixture for 2 hours while stirring at 10 占 폚. The reaction was completed by stirring at 10 ° C. for 30 minutes, and 116 g of water was added and stirred for 30 minutes. The organic layer was separated and vacuum distilled to recover 1,4-dioxane, and 96.4 g of light yellow O-ethyl-S and S-dipropylphosphorodithioate was obtained as a residue. Purity 98% and yield 76% by gas chromatography.
(실시예 4)(Example 4)
노르말프로필메르캅탄 1몰(76.2g)을 테트라하이드로퓨란 150m1에 넣고, 10℃에서 35% 포타시움하이드록사이드 수용액 1몰(160.4g)을 1시간동안 교반하면서 적하하여 노르말프로필메르캅탄소이움염을 합성한다. 상기 반응혼합물에 O-에틸포스포로디클로리데이트 0.5몰(81.3g)을 10℃에서 교반하면서 2시간동안 서서히 적하한다. 10℃에서 1시간동안 교반하여 반응을 완결시키고, 물 120g을 넣고 30분간 교반한다. 유기층을 분리한 후 진공증류하여 테트라하이드로퓨란을 회수하고, 잔류물로 연노랑색의 O-에틸-S, S-디프로필포스포로디티오에이트 94g을 얻었다. 가스크로마토그라피에 의한 순도 98%, 수득율 76%이다.1 mole (76.2 g) of normal propyl mercaptan was added to 150 m 1 of tetrahydrofuran, and 1 mole (160.4 g) of 35% aqueous potassium hydroxide solution was added dropwise while stirring at 10 ° C. for 1 hour to synthesize normal propyl mercaptanium salt. do. 0.5 mol (81.3 g) of O-ethylphosphorodichlorate was slowly added dropwise to the reaction mixture for 2 hours while stirring at 10 占 폚. Stir at 10 ° C. for 1 hour to complete the reaction, add 120 g of water and stir for 30 minutes. The organic layer was separated and vacuum distilled to recover tetrahydrofuran, and 94 g of light yellow O-ethyl-S and S-dipropylphosphorodithioate were obtained as a residue. Purity 98%, yield 76% by gas chromatography.
상술한 바와같이 본원 발명은 물 존재하에서 노르말프로필메르캅탄염과 O-에틸포스포로디티오에이트를 반응시키므로 수용성인 노르말프로필메르캅탄염이 완전히 용해되어 교반이 어려운 문제점을 해결하였고, 유기용제를 사용하지 않기 때문에 생산비용을 저렴하게 할수 있는 잇점을 지녔다. 노르말프로필메르캅탄을 알칼리 수용액보다 과량으로 사용함으로써 미반응 알칼리의 량이 적게하여 알칼리에 약한 O-에틸포스포로디클로리데이트 및 O-에틸-S, S-디프로필포스포로디티오에이트가 분해되는 것을 방지하여 수율을 향상시킬 수 있었고, 과량으로 들어간 노르말프로필메르캅탄이 용매 역할까지 수행하여 세척시에 비중이 낮은 유기용제를 따로 첨가하지 않아도 분액이 명확히 되는 잇점을 지닌다. 또한 노르말프로필메르캅탄염을 O-에틸포스포로디클로리데이트보다 과량으로 사용함으로써 O-에틸포스포로클로리데이트가 물에 의해 분해되는 속도보다 노르말프로필메르캅탄염과 반응하는 속도가 크게하여 수율이 향상되었다.As described above, in the present invention, the reaction of the normal propyl mercaptan salt and O-ethylphosphorodithioate in the presence of water completely solves the problem that the aqueous soluble normal propyl mercaptan salt is completely dissolved and difficult to stir, and an organic solvent is used. It does not have the advantage of lowering the production cost. By using an excess amount of normal propylmercaptan than an aqueous alkali solution, the amount of unreacted alkali is reduced so that O-ethylphosphorodichlorate and O-ethyl-S and S-dipropylphosphorodithioate, which are weak to alkali, are decomposed. It was possible to improve the yield by preventing the excess, normal propylmercaptan entered into the excess of the role of the solvent has the advantage that the separation is clear even without the addition of a low specific gravity organic solvent during washing. In addition, the use of the normal propyl mercaptan salt in excess of the O-ethyl phospho dichlorate, the rate of reaction with the normal propyl mercaptan salt is greater than the rate at which O-ethyl phosphochloridate is decomposed by water, yield This was improved.
Claims (10)
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