KR20040100302A - Process for preparing bomyl derivatives - Google Patents
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- KR20040100302A KR20040100302A KR1020030032597A KR20030032597A KR20040100302A KR 20040100302 A KR20040100302 A KR 20040100302A KR 1020030032597 A KR1020030032597 A KR 1020030032597A KR 20030032597 A KR20030032597 A KR 20030032597A KR 20040100302 A KR20040100302 A KR 20040100302A
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- bomyl
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- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims abstract description 9
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- GLUYADGKGBGXRV-UHFFFAOYSA-N chloro dihydrogen phosphate Chemical compound OP(O)(=O)OCl GLUYADGKGBGXRV-UHFFFAOYSA-N 0.000 claims abstract description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 10
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- BWZHKRSSCFRVIE-UHFFFAOYSA-N 1-n,4-n-dimethyl-2h-pyridine-1,4-diamine Chemical compound CNN1CC=C(NC)C=C1 BWZHKRSSCFRVIE-UHFFFAOYSA-N 0.000 claims 1
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 abstract 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 abstract 2
- 229940043279 diisopropylamine Drugs 0.000 abstract 1
- 230000000749 insecticidal effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229940086542 triethylamine Drugs 0.000 description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RNJOKCPFLQMDEC-UHFFFAOYSA-N 4(R),8-dimethyl-trans-2-nonenoyl-CoA Chemical compound COC(=O)CC(=O)CC(=O)OC RNJOKCPFLQMDEC-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000012039 electrophile Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 241000238876 Acari Species 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- NGFFLHMFSINFGB-UHFFFAOYSA-N [chloro(methoxy)phosphoryl]oxymethane Chemical compound COP(Cl)(=O)OC NGFFLHMFSINFGB-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 2
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 230000008029 eradication Effects 0.000 description 2
- -1 ester compound Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 보밀(Bomyl) 유도체의 개선된 제조방법에 관한 것으로, 특히 트리-케토 에스테르에 친전자체를 선택적으로 산소원자에 부가하는 엔올(enol) 합성반응을 통해 보다 간편하고 온화한 반응조건에서 한 번에 반응을 완료할 수 있는 보밀 유도체 제조 방법에 관한 것이다.The present invention relates to an improved process for the preparation of Bomyl derivatives, in particular through simple and mild reaction conditions through enol synthesis, in which an electrophile is selectively added to an oxygen atom to a tri-keto ester. It relates to a method of preparing a derivative of derivatives capable of completing the reaction.
보밀(Bomyl)은 진드기와 기타 곤충들의 박멸에 뛰어나며, 특히 파리 구제에 널리 사용되고 있다. 종래의 고전적인 보밀 유도체의 합성 방법으로는, 예를 들어 미국 특허 제2,891,887호에 두 가지 방법이 소개되어 있다.Bomyl is excellent for the eradication of ticks and other insects, and is especially used for flies. As a method for synthesizing a conventional classical wheat derivative, two methods are introduced, for example, in US Pat. No. 2,891,887.
첫 번째 방법은, 하기 반응식 1에 나타낸 바와 같이, 화합물 2로 표시되는 트리-케토 에스테르에 나트륨을 넣어 나트륨 에놀레이트를 만들고 여기에 화학식 3으로 표시되는 클로로 포스페이트를 반응시켜 보밀을 얻는 2단계 반응이다. 그러나, 이 반응에서는 화재나 폭발성의 위험 때문에 다루기가 위험하고, 까다로운 나트륨을 써야하고, 반응 중에 수소의 발생이 있으며, 또한 용매는 무수 조건에서 사용해야하므로 대량생산에 어려움이 있다.The first method is a two-step reaction in which sodium is added to a tri-keto ester represented by compound 2 to form sodium enolate, and the chloro phosphate represented by formula 3 is reacted to obtain boil as shown in Scheme 1 below. . However, this reaction is difficult to handle due to the risk of fire or explosiveness, it is difficult to mass-produce due to the use of difficult sodium, the generation of hydrogen during the reaction, and the use of the solvent in anhydrous conditions.
두 번째 방법은 하기 반응식 2에 나타낸 바와 같이, 화학식 2로 표시되는 트리-케토 에스테르에 SO2Cl2를 사용하여 클로로가 치환된 화합물을 미리 제조한 후, 여기에 화학식 4로 표시되는 메틸 포스파이트를 넣어 보밀을 얻는 방법이다. 이 방법은 클로로 화합물을 합성하는 첫 번째 단계에서 인체에 유해한 SO2, HCl 등 가스가 나오고 두 번째 단계에서도 인체에 유해한 클로로메탄 가스가 나온다는 단점 뿐 만이 아니라, 냄새가 심한 메틸 포스파이트를 써야하는 단점이 있다.In the second method, as shown in Scheme 2 below, a compound in which chloro is substituted using SO 2 Cl 2 in the tri-keto ester represented by the formula (2) is prepared in advance, and then methyl phosphite represented by the formula (4) Is how to get boiled. This method not only has the disadvantage of producing harmful gases such as SO 2 and HCl in the first stage of the synthesis of chloro compounds, but also of chloromethane, which is harmful to the human body in the second stage. There is this.
따라서, 본 발명은 상기 종래 기술의 단점을 개선하여 두 단계 반응을 한 단계로 간략화하면서도 SO2, HCl, MeCl 등의 유해한 가스가 방출되는 문제점을 개선한 환경친화적인 보밀 제조 방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide an environmentally friendly process for producing dense, which improves the disadvantages of harmful gases such as SO 2 , HCl, MeCl, etc. while simplifying the two-step reaction in one step by improving the disadvantages of the prior art. It is done.
상기 목적을 달성하기 위하여, 본 발명에서는 트리-케토 에스테르를 염기의 존재하에 클로로포스페이트와 반응시키는 것을 포함하는 보밀 유도체 제조 방법을 제공한다.In order to achieve the above object, the present invention provides a method for preparing a derivative of wheat, comprising reacting a tri-keto ester with chlorophosphate in the presence of a base.
이하 본 발명에 따른 제조방법을 보다 상세히 설명한다.Hereinafter, the manufacturing method according to the present invention will be described in more detail.
본 발명에 따르면, 화학식 1의 보밀 유도체는, 하기 반응식 3에서와 같이, 화학식 2로 표시되는 트리-케토 에스테르와 화학식 3으로 표시되는 클로로 포스페이트를 염기 존재 하에 반응시킴으로써 제조될 수 있다.According to the present invention, the boil derivatives of the formula (1) can be prepared by reacting the tri-keto ester represented by the formula (2) with the chloro phosphate represented by the formula (3) in the presence of a base, as shown in Scheme 3 below.
상기 식에서, R1및 R2는 각각 독립적으로 C1∼ C5의 저급 알킬기이다.In the above formula, R 1 and R 2 are each independently C 1 to C 5 lower alkyl groups.
상기 반응에 사용가능한 염기는 트리에틸아민, 트리메틸아민, 디이소프로필에틸아민, N-메틸모포린, DBU(1,8-디아자비사이클로[5,4,0]운데스-7-엔) 등의 유기 염기들이며, 이 중에서 트리에틸 아민, 트리메틸 아민이 바람직하게 사용할 수있다. 이때 염기는 화학식 2의 화합물 1 당량에 대하여 1.2 내지 3.0 당량, 바람직하게는 1.2 내지 2.0 당량의 양으로 사용할 수 있다. 상기 염기와 함께 DMAP(4-디메틸아미노피리딘)등을 촉매로서 촉매량 사용할 수도 있다.Bases available for the reaction include triethylamine, trimethylamine, diisopropylethylamine, N-methylmorpholine, DBU (1,8-diazabicyclo [5,4,0] undes-7-ene), and the like. Organic bases of which triethyl amine and trimethyl amine can be preferably used. In this case, the base may be used in an amount of 1.2 to 3.0 equivalents, preferably 1.2 to 2.0 equivalents, based on 1 equivalent of the compound of Formula 2. A catalytic amount of DMAP (4-dimethylaminopyridine) or the like may be used together with the base as a catalyst.
상기 반응에서 화학식 3으로 표시되는 클로로 포스페이트는 화학식 2 화합물 1 당량에 대하여 1.2 내지 3.0 당량, 바람직하게는 1.2 내지 1.5 당량의 양으로 사용할 수 있다.In the reaction, chloro phosphate represented by Formula 3 may be used in an amount of 1.2 to 3.0 equivalents, preferably 1.2 to 1.5 equivalents, based on 1 equivalent of Formula 2 compound.
상기 반응은 염기 존재 하에 용매를 사용하여 저온의 반응조건으로 수행하는데, 반응용매로는 통상적인 것을 사용할 수 있으며 바람직하게는 디클로로메탄, 클로로포름, 디클로로에탄 등을 사용할 수 있다. 상기 반응의 온도 범위는 -76 ∼ 0 ℃ 범위이며 바람직하게는 -10℃ 내지 0℃가 적당하다. 반응시간은 1 내지 5 시간이 적당하며 바람직하게는 1 내지 2 시간이다.The reaction is carried out under low temperature reaction conditions using a solvent in the presence of a base, a conventional solvent may be used, preferably dichloromethane, chloroform, dichloroethane and the like. The temperature range of the reaction is in the range of -76 to 0 캜, preferably -10 캜 to 0 캜. The reaction time is suitably 1 to 5 hours, preferably 1 to 2 hours.
이상과 같이, 본 발명에 따르면 트리-케토 에스테르에 염기와 클로로포스페이트와 같은 친전자체를 사용하여 친전자체를 선택적으로 산소원자에 부가하는 엔올(enol) 합성반응을 수행함으로써 보다 간편하고 온화한 반응조건에서 1 단계로 보밀 유도체를 제조할 수 있다.As described above, according to the present invention, by using an electrophile such as base and chlorophosphate to tri-keto ester, an enol synthesis reaction of selectively adding an electrophile to an oxygen atom is performed in a simpler and milder reaction condition. The boil derivatives can be prepared in one step.
이하, 실시예에 의해 본 발명을 보다 상세히 설명하며, 이들 실시예가 본 발명을 제한하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, which do not limit the present invention.
실시예 1 : 보밀(화학식 1에서 RExample 1 Rough (R in Formula 1) 1One , R, R 22 = Me)의 합성= Me)
얼음욕(ice salt bath) 중에서 100mL 3구 둥근바닥 플라스크에 디메틸 1,3-아세톤디카복실레이트(1 g, 5.74 mmol), 디클로로메탄(MC)(무수) 15 mL, 트리에틸아민 (0.872 g, 8.61 mmol) 및 DMAP 촉매량을 넣고 디메틸 클로로포스페이트(1.079 g, 7.46 mmol)를 디클로로메탄 10 ml 에 희석시켜서 적가하였다. 4시간 30분후 반응을 종결하여 물로 두 번 씻어주고 MgSO4를 넣어 수분을 제거한 후 용매를 증발시켜 잔사를 헥산: 에틸아세테이트(EA) 1 : 1의 혼합물을 전개용매(eluent)로 컬럼 크로마토그래피하여 표제 화합물을 수득하였다.In a 100 mL three-necked round bottom flask in an ice salt bath, dimethyl 1,3-acetonedicarboxylate (1 g, 5.74 mmol), 15 mL dichloromethane (MC) (anhydrous), triethylamine (0.872 g, 8.61 mmol) and DMAP catalyst amount were added dropwise by diluting dimethyl chlorophosphate (1.079 g, 7.46 mmol) in 10 ml of dichloromethane. After 4 hours and 30 minutes, the reaction was terminated, washed twice with water, MgSO 4 was added to remove moisture, and the solvent was evaporated. The residue was then purified by column chromatography on a mixture of hexane: ethyl acetate (EA) 1: 1. The title compound was obtained.
수율 : 1.39 g (4.94 mmol, 86 %)Yield: 1.39 g (4.94 mmol, 86%)
1H-NMR(300 MHz, CDCl3) δ 6.03(s, 1H), 3.96(s, 2H), 3.84, 3.88(s, 6H), 3.71, 3.72(s, 6H) 1 H-NMR (300 MHz, CDCl 3 ) δ 6.03 (s, 1H), 3.96 (s, 2H), 3.84, 3.88 (s, 6H), 3.71, 3.72 (s, 6H)
실시예 2 : 보밀 유도체(화학식 1에서 RExample 2: Bomil Derivatives (R in Formula 1 1One = Me, R= Me, R 22 = Et)의 합성= Synthesis of Et)
얼음욕(ice salt bath) 중에서 100mL 3구 둥근바닥 플라스크에 디메틸 1,3-아세톤디카복실레이트(1 g, 5.74 mmol), 디클로로메탄(무수) 15 mL, 트리에틸아민 (0.872 g, 8.61 mmol), 및 DMAP 촉매량을 넣고 디에틸 클로로포스페이트(1.23 g, 7.46 mmol)를 디클로로메탄 10 ml 에 희석시켜서 적가하였다. 1시간 20분후 반응을 종결하여 물로 두 번 씻어주고 CaCl2를 넣어 수분을 제거한 후 용매를 증발시켜 잔사를 헥산: 에틸아세테이트(EA) 1 : 1의 혼합물을 전개용매(eluent)로 컬럼 크로마토그래피하여 표제 화합물을 수득하였다.In a 100 mL three-necked round bottom flask in an ice salt bath, dimethyl 1,3-acetonedicarboxylate (1 g, 5.74 mmol), 15 mL dichloromethane (anhydrous), triethylamine (0.872 g, 8.61 mmol) , And the amount of DMAP catalyst were added and diethyl chlorophosphate (1.23 g, 7.46 mmol) was diluted dropwise in 10 ml of dichloromethane. After 1 hour and 20 minutes, the reaction was terminated, washed twice with water, CaCl 2 was added to remove moisture, and the solvent was evaporated. The residue was then chromatographed with a solvent mixture of hexane: ethyl acetate (EA) 1: 1. The title compound was obtained.
수율 : 1.5071 g (4.86 mmol, 84.6 %)Yield: 1.5071 g (4.86 mmol, 84.6%)
1H-NMR(300 MHz, CDCl3) δ 5.97(s, 1H), 4.10-4.21(q, 4H), 3.89(s, 2H), 3.64, 3.65(s, 6H), 1.28-1.33(t, 6H) 1 H-NMR (300 MHz, CDCl 3 ) δ 5.97 (s, 1H), 4.10-4.21 (q, 4H), 3.89 (s, 2H), 3.64, 3.65 (s, 6H), 1.28-1.33 (t, 6H)
실시예 3 : 보밀 유도체(화학식 1에서 RExample 3 Bovine Derivative (R in Formula 1) 1One =Et, R= Et, R 22 =Me)의 합성Synthesis of = Me)
얼음욕(ice salt bath) 중에서 250mL 3구 둥근바닥 플라스크에 디메틸 1,3-아세톤디카복실레이트(6 g, 29.67 mmol), 디클로로메탄(무수) 40 mL, 트리에틸아민 (4.5 g, 44.51 mmol), 및 DMAP 촉매량을 넣고 디메틸 클로로포스페이트(5.6 g, 38.57 mmol)를 디클로로메탄 40 ml에 희석시켜서 적가하였다. 5시간 후 반응을 종결하여 물로 두 번 씻어주고 MgSO4를 넣어 수분을 제거한 후 용매를 증발시켜 잔사를 헥산: 에틸아세테이트(EA) 1 : 1의 혼합물을 전개용매(eluent)로 컬럼 크로마토그래피하여 표제 화합물을 수득하였다.In a 250 mL three necked round bottom flask in an ice salt bath, dimethyl 1,3-acetonedicarboxylate (6 g, 29.67 mmol), 40 mL dichloromethane (anhydrous), triethylamine (4.5 g, 44.51 mmol) And the amount of DMAP catalyst were added dropwise by diluting dimethyl chlorophosphate (5.6 g, 38.57 mmol) in 40 ml of dichloromethane. After 5 hours, the reaction was terminated, washed twice with water, MgSO 4 was added to remove moisture, and the solvent was evaporated. The residue was then purified by column chromatography on a mixture of hexane: ethyl acetate (EA) 1: 1 with eluent. The compound was obtained.
수율 : 6.7 g (21.6 mmol, 73 %)Yield: 6.7 g (21.6 mmol, 73%)
1H-NMR (300 MHz, CDCl3) δ 5.96(s, 1H), 4.09-4.15(q, 4H), 3.88(s, 2H), 3.78, 3.82(s, 6H), 1.18-1.23(t, 6H) 1 H-NMR (300 MHz, CDCl 3 ) δ 5.96 (s, 1H), 4.09-4.15 (q, 4H), 3.88 (s, 2H), 3.78, 3.82 (s, 6H), 1.18-1.23 (t, 6H)
실시예 4 : 보밀 유도체(RExample 4 Bovine Derivative (R 1One , R, R 22 = Et)의 합성= Synthesis of Et)
얼음욕(ice salt bath) 중에서 250mL 3구 둥근바닥 플라스크에 디메틸 1,3-아세톤디카복실레이트(6 g, 29.67 mmol), 디클로로메탄(무수) 40 mL, 트리에틸아민 (4.5 g, 44.51 mmol), 및 DMAP 촉매량을 넣고 디에틸 클로로포스페이트(6.7 g, 38.57 mmol)를 디클로로메탄 40 ml 에 희석시켜서 적가하였다. 2시간 후 반응을 종결하여 물로 두 번 씻어주고 MgSO4를 넣어 수분을 제거한 후 용매를 증발시켜 잔사를 헥산: 에틸아세테이트(EA) 1 : 1의 혼합물을 전개용매(eluent)로 컬럼 크로마토그래피하여 표제 화합물을 수득하였다.In a 250 mL three necked round bottom flask in an ice salt bath, dimethyl 1,3-acetonedicarboxylate (6 g, 29.67 mmol), 40 mL dichloromethane (anhydrous), triethylamine (4.5 g, 44.51 mmol) And the amount of DMAP catalyst were added and diethyl chlorophosphate (6.7 g, 38.57 mmol) was diluted in 40 ml of dichloromethane and added dropwise. After 2 hours, the reaction was terminated, washed twice with water, MgSO 4 was added to remove moisture, and the solvent was evaporated. The residue was then purified by column chromatography on a mixture of hexane: ethyl acetate (EA) 1: 1 with eluent. The compound was obtained.
수율 : 8.8595 g (26.19 mmol, 88.3 %)Yield: 8.8595 g (26.19 mmol, 88.3%)
1H-NMR (300 MHz, CDCl3) δ 6.03(s, 1H), 4.12-4.27(m, 8H), 3.94(s, 2H), 1.35-1.40(t, 3H), 1.25-1.30(t, 3H) 1 H-NMR (300 MHz, CDCl 3 ) δ 6.03 (s, 1H), 4.12-4.27 (m, 8H), 3.94 (s, 2H), 1.35-1.40 (t, 3H), 1.25-1.30 (t, 3H)
본 발명의 방법에 따라 트리케토 에스테르 화합물과 클로로 포스페이트 화합물을 유기 염기하에 반응시켜 보밀 유도체를 얻는 방법은 반응경로가 간략화되고 유해가스의 방출이 없어 원료비 절감 및 환경 친화적 측면에서 큰 이점이 있으며, 수득된 보밀 유도체는 진드기와 기타 곤충들의 박멸에 뛰어나며, 특히 파리 구제에 유용하게 이용될 수 있다.According to the method of the present invention, a method of obtaining a boil derivative by reacting a triketo ester compound with a chloro phosphate compound under an organic base has a large advantage in terms of reducing raw material costs and environmental friendliness since the reaction route is simplified and there is no emission of harmful gases. The derived wheat derivatives are excellent for eradication of ticks and other insects, and may be particularly useful for fly control.
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