KR950001702B1 - Organotinmalonates derivatives, and process for their preparation - Google Patents
Organotinmalonates derivatives, and process for their preparation Download PDFInfo
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- KR950001702B1 KR950001702B1 KR1019920006404A KR920006404A KR950001702B1 KR 950001702 B1 KR950001702 B1 KR 950001702B1 KR 1019920006404 A KR1019920006404 A KR 1019920006404A KR 920006404 A KR920006404 A KR 920006404A KR 950001702 B1 KR950001702 B1 KR 950001702B1
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- 238000000034 method Methods 0.000 title claims 2
- 238000002360 preparation method Methods 0.000 title description 33
- -1 organo tin malonate Chemical compound 0.000 claims abstract description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 5
- 150000002690 malonic acid derivatives Chemical class 0.000 claims description 15
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 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 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 abstract 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 1
- 229960001701 chloroform Drugs 0.000 abstract 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 33
- 238000002329 infrared spectrum Methods 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 28
- 239000001257 hydrogen Substances 0.000 description 28
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 28
- 238000002844 melting Methods 0.000 description 26
- 230000008018 melting Effects 0.000 description 26
- 238000000921 elemental analysis Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 230000001093 anti-cancer Effects 0.000 description 5
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 description 5
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 5
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 4
- JWRNFZDNZYMTDQ-UHFFFAOYSA-L bis(3-methoxy-3-oxopropyl)tin(2+);dichloride Chemical compound COC(=O)CC[Sn](Cl)(Cl)CCC(=O)OC JWRNFZDNZYMTDQ-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OOINULGMLGNAAR-UHFFFAOYSA-N 2-methylsulfanyloxycarbonylprop-2-enoic acid Chemical compound CSOC(=O)C(=C)C(=O)O OOINULGMLGNAAR-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 3
- RHFTTZVNBAHQBF-UHFFFAOYSA-L dicyclohexyltin(2+);dibromide Chemical compound C1CCCCC1[Sn](Br)(Br)C1CCCCC1 RHFTTZVNBAHQBF-UHFFFAOYSA-L 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- YICRPERKKBDRSP-UHFFFAOYSA-N methyl 3-amino-4-methylthiophene-2-carboxylate Chemical compound COC(=O)C=1SC=C(C)C=1N YICRPERKKBDRSP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000000975 bioactive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- WDQNIWFZKXZFAY-UHFFFAOYSA-M fentin acetate Chemical compound CC([O-])=O.C1=CC=CC=C1[Sn+](C=1C=CC=CC=1)C1=CC=CC=C1 WDQNIWFZKXZFAY-UHFFFAOYSA-M 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000007093 Leukemia L1210 Diseases 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- DQLATGHUWYMOKM-UHFFFAOYSA-L cisplatin Chemical compound N[Pt](N)(Cl)Cl DQLATGHUWYMOKM-UHFFFAOYSA-L 0.000 description 1
- 229960004316 cisplatin Drugs 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- PEGCFRJASNUIPX-UHFFFAOYSA-L ditert-butyltin(2+);dichloride Chemical compound CC(C)(C)[Sn](Cl)(Cl)C(C)(C)C PEGCFRJASNUIPX-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- UFHLMYOGRXOCSL-UHFFFAOYSA-N isoprothiolane Chemical compound CC(C)OC(=O)C(C(=O)OC(C)C)=C1SCCS1 UFHLMYOGRXOCSL-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 244000000003 plant pathogen Species 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XKMVDDSQCAHUSM-UHFFFAOYSA-J propanedioate;tin(4+) Chemical class O1C(=O)CC(=O)O[Sn]21OC(=O)CC(=O)O2 XKMVDDSQCAHUSM-UHFFFAOYSA-J 0.000 description 1
- 229910001415 sodium ion Chemical group 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- SBXWFLISHPUINY-UHFFFAOYSA-N triphenyltin Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)C1=CC=CC=C1 SBXWFLISHPUINY-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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Description
본 발명은 다음 일반식(Ⅰ)로 표시되는 신규한 유기주석 말로네이트 유도체 및 그 제조방법을 제공한다.The present invention provides a novel organotin malonate derivative represented by the following general formula (I) and a preparation method thereof.
상기 일반식(Ⅰ)에 있어서 R은 페닐, 시클로헥실, n-부틸, 3-메톡시-3-옥소프로필, 메틸, t-부틸, 염소기등을, x는 2 또는 3을, R`는 비고리치환기가 치환될 때에는 티오메톡시, 메틸기를, 고리치환기가 치환될 때에는 에틸렌디티오, 메틸렌디티오, 아세틸렌디티오기를 표시한다. 본 발명의 일반식(Ⅰ)의 유지주석 말로네이트 유도체는 살균 및 항암잠재력을 갖는 유용한 신규 화합물이다.In general formula (I), R is phenyl, cyclohexyl, n-butyl, 3-methoxy-3-oxopropyl, methyl, t-butyl, a chlorine group, x is 2 or 3, R 'is When the acyclic substituent is substituted, the thiomethoxy and methyl group are substituted, and when the ring substituent is substituted, the ethylenedithio, methylenedithio and acetylenedithio group are represented. The oil-in-water malonate derivatives of general formula (I) of the present invention are useful novel compounds having bactericidal and anticancer potential.
일반적으로 카르복실 리간드를 포함하는 유기주석 화합물은 생리활성을 갖는 유용한 물질로 연구가 매우 활발히 진행되고 있는 분야이다. 예로서, 트리페닐주석 아세테이트In general, organotin compounds containing carboxyl ligands are useful materials having physiological activities and are being actively studied. As an example, triphenyltin acetate
는 ＂Brestan＂(Hoechst사)이라는 상품명으로 현재 시판되는 살균제이다.(J. Organomet. Chem. Lib. 16, 1985). 더우기 최근의 연구결과(Metal-Based Anti-tumor Drug, P.103, Freund Publishing House LTD, 1988)에 의하면 디알킬주석 카르보실레이트 계열의 화합물들이 시험관(in vitro) 시험에서 시스플라틴보다 우수한 항암효과를 나타내고 있다고 한다.Is a fungicide currently marketed under the trade name Brestan® (Hoechst) (J. Organomet. Chem. Lib. 16, 1985). Furthermore, recent studies (Metal-Based Anti-tumor Drug, P. 103, Freund Publishing House LTD, 1988) show that dialkyltin carbosylated compounds have superior anti-cancer effects in vitro to cisplatin. It is said to indicate.
한편 말로네이트 유도체중에 다음 구조식의 말로틸레이트는 만성적 간질환 치료제(U.S. Pat. 4327223(1982))로서 유용하게 사용되고In the malonate derivative, malotylate of the following structural formula is usefully used as a therapeutic agent for chronic liver disease (U.S. Pat. 4327223 (1982)).
있을 뿐만 아니라 다음 구조의 화합물(상품명 : Fujione)은 살균제로도 유명하다(Prod. Insectic. Fungic. Conf., 8th, 1975, 2, 715).In addition, the compound of the following structure (trade name: Fujione) is also known as a fungicide (Prod. Insectic. Fungic. Conf., 8th, 1975, 2, 715).
이상에서와 같이 유기주석 카르복실레이트 및 말로네이트 유도체들이 유용한 생리활성 물질로 사용되고 있지만 모든 물질이 그러하듯이 일정기간동안 사용하면 이에 대한 내항성의 균종이 생겨 그 효과가 점차 감소되고 있기 때문에 그 대체품이 요구되고 있는 실정이다.As mentioned above, organotin carboxylate and malonate derivatives are used as useful bioactive substances, but as all substances are used for a certain period of time, the resistant species against them are formed and the effect is gradually reduced. It is a required situation.
본 발명자들은 종래의 유기주석 화합물들의 문제점들을 보완하는 새로운 생리활성물질을 개발하고자 연구를 계속하던차 더욱 강력한 살균력을 갖거나 실용성있는 항암효과가 기대되는 신규한 일반식(Ⅰ)의 유기주석 말로네이트 유도체를 발견하게 되었다.The inventors of the present invention continue to develop new bioactive substances that complement the problems of conventional organotin compounds. The organic tin malonate derivatives of the general formula (I), which are expected to have more powerful bactericidal or practical anticancer effects Was found.
본 발명의 제조에 관해 간단히 설명하면, 일반식(Ⅱ)의 유기주석 할라이드와 말로네이트 유도체의 에스테르를 가수분해하여 생성된 일반식(Ⅲ)의 말로네이트 유도체의 금속염을 적절한 몰비로 반응시켜서 일반식(Ⅰ)의 유기주석 말로네이트 유도체를 제조하는 것이다.Briefly describing the preparation of the present invention, the metal salt of the malonate derivative of the general formula (III) produced by hydrolysis of the ester of the organotin halide of the general formula (II) and the malonate derivative is reacted in an appropriate molar ratio The organotin malonate derivative of (I) is manufactured.
일반식(Ⅱ)에 있어서 R은 페닐, 시클로헥실, n-부틸, 3-메톡시-3-옥소프로필, 메틸, t-부틸, 염소기등을, x는 2 혹은 3을, X는 염소 또는 브롬을 표시한다.In general formula (II), R is phenyl, cyclohexyl, n-butyl, 3-methoxy-3-oxopropyl, methyl, t-butyl, a chlorine group, x is 2 or 3, X is chlorine or Display bromine.
일반식(Ⅲ)에 있어서 M은 칼륨 혹은 나트륨 이온을, R`는 일반식(Ⅰ)의 것과 동일하다.In general formula (III), M is potassium or sodium ion, and R 'is the same as that of general formula (I).
일반식(Ⅲ)의 말로네이트 유도체의 금속염을 공지문헌(Acta Chem. Scand, 1968, 22, 1107; Chem. Pharm. Bull. 1990, 30, 3242)에 따라서 제조하거나 상품화된 에스테르를 직접 구입해서 알칼리 존재하에서 다음과 같은 표준방법으로 가수분해하면 얻어진다.Metal salts of malonate derivatives of general formula (III) were prepared according to the known literature (Acta Chem. Scand, 1968, 22, 1107; Chem. Pharm. Bull. 1990, 30, 3242) It is obtained by hydrolysis in the presence of the following standard methods.
본 발명의 제조방법을 보다 자세히 설명하면, 일반식(Ⅱ)의 유기주석 할라이드와 일반식(Ⅲ)의 말로네이트 유도체의 금속염을 아래의 적당한 용매와 함께 -25℃ 내지는 60℃에서 바로 교반시키거나 어느 한쪽을 적가시킨후 3시간-4시간동안 교반시켰다. 부산물인 할로겐염을 걸러서 제거한후 감압하에서 용매를 증발시키면 흰색 또는 엷은 노랑색의 고체 또는 점도가 높은 액체가 높은 수율(80% 이상)로 생성되는데 이를 직접 분광학적 방법 및 원소분석법에 의해 확인하거나 필요한 경우 적절한 용매에 재결정하여 일반식(Ⅰ)의 유기주석 말로네이트 유도체를 얻는다. 이 때 반응에 사용되는 용매로는 디클로로메탄, 클로로포름 외에 에틸알콜, 메틸알콜, 아세톤, 물 등을 사용하거나 필요에 따라서는 이 용매들의 혼합용매를 사용해도 무방하다. 반응온도는 넓은 범위(-25℃∼60℃)가 가능하나 23±2℃에서의 반응이 가장 편리하다.In more detail, the metal salts of organotin halides of formula (II) and malonate derivatives of formula (III) are stirred directly at -25 ° C or 60 ° C with the following suitable solvents. Either one was added dropwise and stirred for 3-4 hours. When the by-product halogen salt is filtered off and the solvent is evaporated under reduced pressure, a white or pale yellow solid or a high viscosity liquid is produced in high yield (more than 80%), which can be directly confirmed by spectroscopic or elemental analysis or Recrystallization in a suitable solvent gives an organotin malonate derivative of general formula (I). In this case, as the solvent used in the reaction, ethyl alcohol, methyl alcohol, acetone, water, etc. may be used in addition to dichloromethane and chloroform, or a mixed solvent of these solvents may be used, if necessary. The reaction temperature can be a wide range (-25 ℃ ~ 60 ℃), but the reaction at 23 ± 2 ℃ is most convenient.
본 발명에 의해 제조된 일반식(Ⅰ)의 화합물들중 대표적인 화합물, (Ph3Sn)2(OOC)2C=C(SMe)2(표1) 및 {(n-Bu)3Sn}2(OOC)2C=C(SMe)2(표2)의 몇가지 식물병균에 대한 시험관(in vitro) 시험에서의 살균시험 결과는 매우 낮은 농도에서도 상당한 저지율을 보이고 있다.Representative compounds of the compounds of general formula (I) prepared by the present invention, (Ph 3 Sn) 2 (OOC) 2 C = C (SMe) 2 (Table 1) and {(n-Bu) 3 Sn} 2 The results of bactericidal tests in vitro on several plant pathogens of (OOC) 2 C = C (SMe) 2 (Table 2) show significant inhibition at very low concentrations.
[표 1]TABLE 1
(Ph3Sn)2(OOC)2C=C(SMe)2의 살균시험결과Sterilization test results of (Ph 3 Sn) 2 (OOC) 2 C = C (SMe) 2
[표 2]TABLE 2
{(n-Bu)3Sn}2(OOC)2C=C(SMe)2의 살균시험결과Sterilization test results of {(n-Bu) 3 Sn} 2 (OOC) 2 C = C (SMe) 2
여기서 저지율은 전문자료(식물병리실험법, p.638, 일본식물방역협회, 동경, 1961)에 의하였다. 한편 본 발명 화합물들중 몇가지 화합물들에 대한 mouse leukemia L1210에 대한 시험관(in vitro) 시험 항암시험결과는 다음 표3과 같다.The inhibition rate was based on specialized data (Plan Pathology, p.638, Japan Plant Protection Association, Tokyo, 1961). Meanwhile, in vitro test anticancer test results of mouse leukemia L1210 for some of the compounds of the present invention are shown in Table 3 below.
[표 3]TABLE 3
항암효과 시험결과Anticancer effect test result
다음 실시예 에는 본 발명을 자세히 예시한 것으로서 특허청구 범위를 이탈하지 않은 한 다음 실시예에 한정되지 않는다.The following examples illustrate the present invention in detail and are not limited to the following examples unless they depart from the claims.
[실시예 1]Example 1
비스(트리페닐주석)비스(메틸티오)메틸렌말로네이트의 제조Preparation of bis (triphenyltin) bis (methylthio) methylenemalonate
트리페닐주석클로라이드 3.85g(10mmol)과 K2(O2C)2C=C(SCH3)22H2O 1.58g(5mmol)을 디클로로메탄 40ml에 넣고 23±2℃에서 3시간동안 교반한다. 생성된 고체는 걸러서 제거하고 여액의 용매를 감압(10mmHg)하에서 증발시키면 흰색의 고체 3.85g(85%)이 얻어진다. 필요한 경우 이 고체를 디클로로메탄-에틸알콜(1 : 2) 혼합용매에서 재결정하면 무색의 결정성 고체로 얻어진다.3.85 g (10 mmol) of triphenyltin chloride and 1.58 g (5 mmol) of K 2 (O 2 C) 2 C = C (SCH 3 ) 2 2H 2 O were added to 40 ml of dichloromethane and stirred at 23 ± 2 ° C. for 3 hours. . The resulting solids were filtered off and the solvent in the filtrate was evaporated under reduced pressure (10 mmHg) to yield 3.85 g (85%) of a white solid. If necessary, this solid is recrystallized from a dichloromethane-ethyl alcohol (1: 2) mixed solvent to obtain a colorless crystalline solid.
녹는점 : 127±2℃Melting Point: 127 ± 2 ℃
원소분석치(계산치) : C,55.70(55.67) ; H, 3.98(4.00).Elemental Analysis Value (calculated): C, 55.70 (55.67); H, 3.98 (4.00).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.2(s, 6H),7.2-7.7(m, 30H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.2 (s, 6H), 7.2-7.7 (m, 30H).
적외선스펙트럼(KBr,cm-1) : ν(C-O), 1645.Infrared spectrum (KBr, cm -1 ): ν (CO), 1645.
[실시예 2]Example 2
비스(트리시클로헥실주석)비스(메틸티오)메틸렌말로네이트의 제조Preparation of bis (tricyclohexyl tin) bis (methylthio) methylenemalonate
트리시클로헥실주석클로라이드와 K2(C2C)2C=C(SCH3)2·H2O를 실시예 1에서와 같은 방법으로 반응시키면 흰색의 고체가 87%의 수율로 얻어진다.When tricyclohexyl tin chloride was reacted with K 2 (C 2 C) 2 C═C (SCH 3 ) 2 H 2 O in the same manner as in Example 1, a white solid was obtained in a yield of 87%.
녹는점 : 107±1℃Melting Point: 107 ± 1 ℃
원소분석치(계산치) : C, 54,90(53.52) ; H, 7.21(7.70).Elemental analysis value (calculated): C, 54,90 (53.52); H, 7.21 (7.70).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.2-2.3(br, 66H), 2.4(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.2-2.3 (br, 66H), 2.4 (s, 6H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1645.Infrared spectrum (KBr, cm -1 ): ν (CO), 1645.
[실시예 3]Example 3
비스(트리-n-부틸주석)비스(메틸티오)메틸렌말로네이트의 제조Preparation of Bis (tri-n-butyltin) bis (methylthio) methylenemalonate
트리-n-부틸주석클로라이드와 K2(O2C)2C=C(SCH3)2·2H2O를 실시예 1에서와 같이 반응시키면 무색의 점도가 높은 액체가 90%의 수율로 얻어진다.When tri-n-butyltin chloride was reacted with K 2 (O 2 C) 2 C = C (SCH 3 ) 2 .2H 2 O as in Example 1, a colorless high viscosity liquid was obtained in a yield of 90%. Lose.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 0.7-1.9(m, 54H), 2.4(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 0.7-1.9 (m, 54H), 2.4 (s, 6H).
적외선스펙트럼(KBr cell, cm-1) : ν(C-O), 1634.Infrared spectrum (KBr cell, cm −1 ): ν (CO), 1634.
[실시예 4]Example 4
디페닐주석비스(메틸티오)메틸렌말로네이트의 제조Preparation of diphenyltin bis (methylthio) methylenemalonate
디페닐주석클로라이드 1.72g(5mmol)과 K2(O2C)2C=C(SCH3)2·2H2O 1.58g(5mmol)을 디클로로메탄 50ml에 넣고 3시간동안 교반시킨다. 생성된 고체는 걸러서 제거하고 여액의 용매를 감압(10mmHg)하에서 증발시키면 흰색의 고체 2.01g(84% 수율)이 얻어진다.1.72 g (5 mmol) of diphenyltin chloride and 1.58 g (5 mmol) of K 2 (O 2 C) 2 C = C (SCH 3 ) 2 .2H 2 O were added to 50 ml of dichloromethane and stirred for 3 hours. The resulting solids were filtered off and the solvent of the filtrate was evaporated under reduced pressure (10 mmHg) to yield 2.01 g (84% yield) of a white solid.
녹는점 : 210℃ 이상.Melting Point: 210 ℃ or higher.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 2.4(d, 6H), 7.4-8.0(m, 10H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 2.4 (d, 6H), 7.4-8.0 (m, 10H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1628.Infrared spectrum (KBr, cm −1 ): ν (CO), 1628.
[실시예 5]Example 5
디시클로헥실주석비스(메틸티오)메틸렌말로네이트의 제조Preparation of dicyclohexyl tin bis (methylthio) methylenemalonate
디시클로헥실주석디브로마이드와 K2(O2C)2C=C(SCH3)2·2H2O를 실시예 4와 동일한 방법으로 합성하면 흰색의 고체가 82%의 수율로 얻어진다.When dicyclohexyl tin dibromide and K 2 (O 2 C) 2 C = C (SCH 3 ) 2 .2H 2 O were synthesized in the same manner as in Example 4, a white solid was obtained in a yield of 82%.
녹는점 :163±3℃.Melting Point: 163 ± 3 ℃.
원소분석치(계산치) : C, 44.40(44.04) ; 5.95(5.75).Elemental analysis value (calculated): C, 44.40 (44.04); 5.95 (5.75).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.0-2.3(br, 22H), 2.4(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.0-2.3 (br, 22H), 2.4 (s, 6H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1597.Infrared spectrum (KBr, cm −1 ): ν (CO), 1597.
[실시예 6]Example 6
디-n-부틸주석비스(메틸티오)메틸렌말로네이트의 제조Preparation of Di-n-butyltinbis (methylthio) methylenemalonate
디-n-부틸주석디클로라이드와 K2(O2C)2C=C(SCH3)2·2H2O를 실시예 4에서와 같이 합성하면 흰색 고체가 86% 수율로 얻어진다.Synthesis of di-n-butyltindichloride and K 2 (O 2 C) 2 C = C (SCH 3 ) 2 .2H 2 O as in Example 4 yields a white solid in 86% yield.
녹는점 : 64±2℃Melting Point: 64 ± 2 ℃
원소분석치(계산치) : C, 37.70(38.29) ; 5.58(5.51).Elemental analysis value (calculated): C, 37.70 (38.29); 5.58 (5.51).
수소핵자기공명스펙트럼(CDCl3),δ(ppm) : 1.7-2.0(m, 18H), 2.4(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.7-2.0 (m, 18H), 2.4 (s, 6H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1562.Infrared spectrum (KBr, cm −1 ): ν (CO), 1562.
[실시예 7]Example 7
디(3-메톡시-3-옥소프로필)주석비스(메틸티오)메틸렌말로네이트의 제조Preparation of Di (3-methoxy-3-oxopropyl) tinbis (methylthio) methylenemalonate
디(3-메톡시-3-옥소프로필)주석디클로라이드와 K2(O2C)2C=C(SCH3)2·2H2O를 실시예 4에서와 같이 합성하면 흰색의 고체가 85% 수율로 얻어진다.Di (3-methoxy-3-oxopropyl) tindichloride and K 2 (O 2 C) 2 C = C (SCH 3 ) 2 .2H 2 O were synthesized as in Example 4, yielding a white solid. Obtained in% yield.
녹는점 : 81.5±1.5℃Melting Point: 81.5 ± 1.5 ℃
원소분석치(계산치) : 32.50(33.69) ; 3.88(4.04).Elemental analysis value (calculated value): 32.50 (33.69); 3.88 (4.04).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.8(t, 4H), 2.3(s, 6H), 2.8(t, 4H), 3.7(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.8 (t, 4H), 2.3 (s, 6H), 2.8 (t, 4H), 3.7 (s, 6H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1636.Infrared spectrum (KBr, cm −1 ): ν (CO), 1636.
[실시예 8]Example 8
디메틸주석비스(메틸티오)메틸렌말로네이트의 제조Preparation of Dimethyl Tin Bis (methylthio) methylenemalonate
티메틸주석디클로라이드와 K2(O2C)2C=C(SCH3)2·2H2O를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 84% 수율로 얻어진다.Thimethyltindichloride and K 2 (O 2 C) 2 C = C (SCH 3 ) 2 .2H 2 O were synthesized in the same manner as in Example 4 to obtain a white solid in 84% yield.
녹는점 :200℃(분해)Melting Point: 200 ℃ (Decomposition)
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 0.7(s, 6H), 2.3(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 0.7 (s, 6H), 2.3 (s, 6H).
적외선스펙트럼(KBr,cm-1) : ν(C-O), 1564.Infrared spectrum (KBr, cm -1 ): ν (CO), 1564.
[실시예 9]Example 9
디-t-부틸주석비스(메틸티오)메틸렌말로네이트의 제조Preparation of Di-t-butyltinbis (methylthio) methylenemalonate
디-t-부틸주석디클로라이드와 K2(O2C)2C=C(SCH3)2·2H2O를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 82% 수율로 얻어진다.Synthesis of di-t-butyltindichloride and K 2 (O 2 C) 2 C = C (SCH 3 ) 2 .2H 2 O in the same manner as in Example 4 gave a white solid in 82% yield. .
녹는점 : 210℃ 이상.Melting Point: 210 ℃ or higher.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.4(s, 18H), 2.4(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.4 (s, 18H), 2.4 (s, 6H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1630.Infrared spectrum (KBr, cm −1 ): ν (CO), 1630.
[실시예 10]Example 10
비스(트리페닐주석)-1, 3-디티올란-2-일리덴말로네이트의 제조Preparation of Bis (triphenyltin) -1, 3-dithiolane-2-ylidenemalonate
K2(O2C)2C=C(SCH2)2·C2H5OH 1.63g(5mmol)을 에틸알콜 30ml에 균일하게 서스펜션시켜서 트리페닐주석클로라이드 3.85g(10mmol)을 아세톤 30ml에 녹인 용액에 적가시킨 후 23±2℃에서 3시간동안 교반한다. 용매를 감압(10mmHg)하에서 30ml로 줄인후 격렬한 교반과 함께 증류수 100ml를 가하여 생성물은 침전시키고 염화칼륨은 녹인후 걸러서 건조시키면 흰색의 고체 3.84g(85% 수율)이 얻어진다.1.63 g (5 mmol) of K 2 (O 2 C) 2 C = C (SCH 2 ) 2 C 2 H 5 OH was uniformly suspended in 30 ml of ethyl alcohol, and 3.85 g (10 mmol) of triphenyltin chloride was dissolved in 30 ml of acetone. After dropwise addition to the solution, the mixture was stirred at 23 ± 2 ° C. for 3 hours. The solvent was reduced to 30 ml under reduced pressure (10 mmHg), and 100 ml of distilled water was added with vigorous stirring to precipitate the product, and the potassium chloride was dissolved and filtered and dried to give 3.84 g (85% yield) of a white solid.
녹는점 : 164±1℃(분해).Melting point: 164 ± 1 ℃ (decomposition).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 3.4(s, 4H), 7.2-7.9(m, 30H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 3.4 (s, 4H), 7.2-7.9 (m, 30H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1651.Infrared spectrum (KBr, cm −1 ): ν (CO), 1651.
[실시예 11]Example 11
비스(트리시클로헥실주석)-1, 3-디티올란-2-일리덴말로네이트의 제조Preparation of bis (tricyclohexyl tin) -1, 3-dithiolane-2-ylidenemalonate
트리시클로헥실주석클로라이드와 K2(O2C)2C=C(SCH2)2·C2H5OH를 실시예 1과 같은 방법으로 합성하면 흰색의 고체가 87% 수율로 얻어진다.Tricyclohexyl tin chloride and K 2 (O 2 C) 2 C = C (SCH 2 ) 2 C 2 H 5 OH in the same manner as in Example 1 to obtain a white solid in 87% yield.
녹는점 : 137.5±5℃Melting Point: 137.5 ± 5 ℃
원소분석치(계산치) : C, 52.80(53.64) ; H, 7.28(7.50).Elemental analysis value (calculated): C, 52.80 (53.64); H, 7.28 (7.50).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.2-2.3(m, 66H), 3.3(s, 4H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.2-2.3 (m, 66H), 3.3 (s, 4H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1617.Infrared spectrum (KBr, cm −1 ): ν (CO), 1617.
[실시예 12]Example 12
비스(트리-n-부틸주석)-1, 3-디티올란-2-일리덴말로네이트의 제조Preparation of Bis (tri-n-butyltin) -1, 3-dithiolane-2-ylidenemalonate
트리-n-부틸주석클로라이드와 K2(O2C)2C=C(SCH2)2·C2H5OH를 실시예 1에서와 같이 합성하면 엷은 노랑색의 점도가 높은 액체가 90% 수율로 얻어진다.When tri-n-butyltin chloride and K 2 (O 2 C) 2 C = C (SCH 2 ) 2 C 2 H 5 OH were synthesized as in Example 1, the pale yellow high viscosity liquid was 90% yield. Is obtained.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.7-2.9(m, 54H),3.2(s, 4H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.7-2.9 (m, 54H), 3.2 (s, 4H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1522.Infrared spectrum (KBr, cm −1 ): ν (CO), 1522.
[실시예 13]Example 13
디페닐주석-1,3-디티올란-2-일리덴말로네이트의 제조Preparation of Diphenyltin-1,3-dithiolane-2-ylidenemalonate
디페닐주석클로라이드와 K2(O2C)2C=C(SCH2)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 84%의 수율로 얻어진다.Diphenyltin chloride and K 2 (O 2 C) 2 C═C (SCH 2 ) 2 · C 2 H 5 OH were synthesized in the same manner as in Example 4 to obtain a white solid in a yield of 84%.
녹는점 :210℃ 이상.Melting Point: 210 ℃ or higher.
원소분석치(계산치) : 44.20(25.22) ; 3.13(3.37).Elemental analysis value (calculated): 44.20 (25.22); 3.13 (3.37).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 3.0(s, 4H), 7.1-8.0(m, 10H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 3.0 (s, 4H), 7.1-8.0 (m, 10H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1521.Infrared spectrum (KBr, cm −1 ): ν (CO), 1521.
[실시예 14]Example 14
디시클로헥실주석-1, 3-디티올란-2-일리덴말로네이트의 제조Preparation of Dicyclohexyl Tin-1, 3-Dithiolane-2-ylidenemalonate
디시클로헥실주석디브로마이드와 K2(O2C)2C=C(SCH2)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 82%의 수율로 생성된다.When dicyclohexyl tin dibromide and K 2 (O 2 C) 2 C = C (SCH 2 ) 2 C 2 H 5 OH were synthesized in the same manner as in Example 4, a white solid was produced in a yield of 82%. do.
녹는점 :210℃ 이상.Melting Point: 210 ℃ or higher.
원소분석치(계산치) : C, 43.10(44.28) ; 5.51(5.37).Elemental analysis value (calculated): C, 43.10 (44.28); 5.51 (5.37).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.0-2.5(br, 22H), 3.4(d, 4H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.0-2.5 (br, 22H), 3.4 (d, 4H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1539.Infrared spectrum (KBr, cm −1 ): ν (CO), 1539.
[실시예 15]Example 15
디-n-부틸주석-1, 3-디티올란-2-일리덴말로네이트의 제조Preparation of Di-n-butyltin-1, 3-dithiolane-2-ylidenemalonate
디-n-부틸주석클로라이드와 K2(O2C)2C=C(SCH2)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 86%의 수율로 얻어진다.When di-n-butyltin chloride and K 2 (O 2 C) 2 C = C (SCH 2 ) 2 C 2 H 5 OH were synthesized in the same manner as in Example 4, a white solid was obtained in a yield of 86%. Obtained.
녹는점 ; 132±0.5℃이상.Melting point; 132 ± 0.5 ℃ or more.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 0.7-1.9(m, 18H), 3.4(s, 4H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 0.7-1.9 (m, 18H), 3.4 (s, 4H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1543Infrared spectrum (KBr, cm -1 ): ν (CO), 1543
[실시예 16]Example 16
디(3-메톡시-3-옥소프로필)주석-1,3-디티올란-2-일리덴말로네이트의 제조Preparation of Di (3-methoxy-3-oxopropyl) tin-1,3-dithiolane-2-ylidenemalonate
디(3-메톡시-3-옥소프로필)주석디클로라이드와 K2(O2C)2C=C(SCH2)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 83%의 수율로 얻어진다.When di (3-methoxy-3-oxopropyl) tindichloride and K 2 (O 2 C) 2 C = C (SCH 2 ) 2 C 2 H 5 OH were synthesized in the same manner as in Example 4, white Solid is obtained in 83% yield.
녹는점 : 95℃(분해)Melting Point: 95 ℃ (Decomposition)
원소분석치(계산치) : C, 32.30(33.82) ; H, 3.85(3.65).Elemental analysis value (calculated): C, 32.30 (33.82); H, 3.85 (3.65).
수소핵자기공명스펙트럼(CDCl3),δ(ppm) : 1.8(t, 4H), 2.8(t, 4H), 3.3(s, 4H), 3.7(s, 6H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.8 (t, 4H), 2.8 (t, 4H), 3.3 (s, 4H), 3.7 (s, 6H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1546Infrared spectrum (KBr, cm -1 ): ν (CO), 1546
[실시예 17]Example 17
디클로로주석-1, 3-디티올란-2-일리덴말로네이트의 제조Preparation of Dichlorotin-1, 3-dithiolane-2-ylidenemalonate
증류수 50ml에 녹인 K2(O2C)2C=C(SCH2)2·C2H5OH 1.64g(5mmol)을 SnCl4·5H2O 1.75g(5mmol)의 50ml 수용액에 교반과 함께 적가한후 23±2℃에서 2시간 더 교반시킨다. 생성된 침전물을 걸러서 에틸알콜로 씻은후 건조시키면 불용성의 흰색의 고체 1.65g(84% 수율)이 얻어진다.1.64 g (5 mmol) of K 2 (O 2 C) 2 C = C (SCH 2 ) 2 C 2 H 5 OH dissolved in 50 ml of distilled water was stirred with 50 ml aqueous solution of 1.75 g (5 mmol) of SnCl 4 .5H 2 O, After the dropwise addition, the mixture is further stirred at 23 ± 2 ° C for 2 hours. The resulting precipitate was filtered, washed with ethyl alcohol and dried to yield 1.65 g (84% yield) of an insoluble white solid.
녹는점 : 120℃(분해).Melting point: 120 ° C (decomposition).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1632.Infrared spectrum (KBr, cm -1 ): ν (CO), 1632.
[실시예 18]Example 18
비스(트리페닐주석)-1, 2-디티올-2-일리덴말로네이트의 제조Preparation of Bis (triphenyltin) -1, 2-dithiol-2-ylidenemalonate
트리페닐주석클로라이드와 K2(O2C)C=C(SCH)2·C2H5OH를 실시예 10에서와 같은 방법으로 합성하면 흰색의 고체가 87%의 수율로 얻어진다.When triphenyltin chloride and K 2 (O 2 C) C═C (SCH) 2 · C 2 H 5 OH were synthesized in the same manner as in Example 10, a white solid was obtained in a yield of 87%.
녹는점 :84±1℃.Melting Point: 84 ± 1 ℃.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 7.1-7.8(m, 32H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 7.1-7.8 (m, 32H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1660Infrared spectrum (KBr, cm -1 ): ν (CO), 1660
[실시예 19]Example 19
비스(트리시클로헥실주석)-1, 3-디티올-2-일리덴말로네이트의 제조Preparation of bis (tricyclohexyl tin) -1, 3-dithiol-2-ylidenemalonate
트리시클로헥실주석클로라이드와 K2(O2C)C=C(SCH)2·C2H5OH를 실시예 10에서와 같은 방법으로 합성하면 흰색의 고체가 87%의 수율로 얻어진다.When tricyclohexyl tin chloride and K 2 (O 2 C) C = C (SCH) 2 .C 2 H 5 OH were synthesized in the same manner as in Example 10, a white solid was obtained in a yield of 87%.
녹는점 :120±2℃.Melting Point: 120 ± 2 ℃.
원소분석치(계산치) : C, 52.90(53.75) ; H, 7.20(7.30).Elemental analysis value (calculated value): C, 52.90 (53.75); H, 7.20 (7.30).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.1-2.1(br, 66H), 7.7(s, 2H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.1-2.1 (br, 66H), 7.7 (s, 2H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1557.Infrared spectrum (KBr, cm −1 ): ν (CO), 1557.
[실시예 20]Example 20
비스(트리-n-부틸주석)-1, 3-디티올-2-일리덴말로네이트의 제조Preparation of Bis (tri-n-butyltin) -1, 3-dithiol-2-ylidenemalonate
트리-n-부틸주석클로라이드와 K2(O2C)C=C(SCH)2·C2H5OH를 실시예 1에서와 같은 방법으로 합성하면 엷은 노랑색의 점도가 높은 액체가 91%의 수율로 얻어진다.When tri-n-butyltin chloride and K 2 (O 2 C) C = C (SCH) 2 C 2 H 5 OH were synthesized in the same manner as in Example 1, a pale yellow high viscosity liquid was 91%. Obtained in yield.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 0.7-1.9(m,54H), 7.0(s,2H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 0.7-1.9 (m, 54H), 7.0 (s, 2H).
적외선스펙트럼(KBr cell, cm-1) : ν(C-O), 1518.Infrared spectrum (KBr cell, cm −1 ): ν (CO), 1518.
[실시예 21]Example 21
디페닐주석-1, 3-디티올-2-일리덴말로네이트의 제조Preparation of Diphenyltin-1, 3-dithiol-2-ylidenemalonate
디페닐주석클로라이드와 K2(O2C)C=C(SCH)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 86%의 수율로 얻어진다.Diphenyltin chloride and K 2 (O 2 C) C═C (SCH) 2 · C 2 H 5 OH were synthesized in the same manner as in Example 4 to obtain a white solid in a yield of 86%.
녹는점 : 140℃(분해)Melting Point: 140 ℃ (Decomposition)
원소분석치(계산치) : C, 45.10(45.51) ; H, 2.60(2.55).Elemental analysis value (calculated): C, 45.10 (45.51); H, 2.60 (2.55).
수소핵자기공명스펙트럼(CMSO-d6), δ(ppm) : 7.2-7.9(m, 12H).Hydrogen nuclear magnetic resonance spectrum (CMSO-d 6 ), δ (ppm): 7.2-7.9 (m, 12H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1514.Infrared spectrum (KBr, cm −1 ): ν (CO), 1514.
[실시예 22]Example 22
디시클로헥실주석-1, 3-디티올-2-일리덴말로네이트의 제조Preparation of Dicyclohexyl Tin-1, 3-dithiol-2-ylidenemalonate
디시클로헥실주석브로마이드와 K2(O2C)C=C(SCH)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 흰색의 불용성 고체가 87%의 수율로 얻어진다.Dicyclohexyl tin bromide and K 2 (O 2 C) C = C (SCH) 2 .C 2 H 5 OH were synthesized in the same manner as in Example 4 to obtain a white insoluble solid in a yield of 87%.
녹는점 : 205℃(분해)Melting Point: 205 ℃ (Decomposition)
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1559.Infrared spectrum (KBr, cm −1 ): ν (CO), 1559.
[실시예 23]Example 23
디-n-부틸주석-1, 3-디티올-2-일리덴말로네이트의 제조Preparation of Di-n-butyltin-1, 3-dithiol-2-ylidenemalonate
디-n-부틸주석디클로라이드와 K2(O2C)C=C(SCH)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 엷은 노랑색의 고체가 87%의 수율로 얻어진다.Di-n-butyltindichloride and K 2 (O 2 C) C = C (SCH) 2 · C 2 H 5 OH were synthesized in the same manner as in Example 4 to give pale yellow solid in 87% yield. Obtained.
녹는점 : 89±1℃Melting Point: 89 ± 1 ℃
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 0.7-2.0(m, 18H), 7.2(s, 2H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 0.7-2.0 (m, 18H), 7.2 (s, 2H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1543.Infrared spectrum (KBr, cm −1 ): ν (CO), 1543.
[실시예 24]Example 24
디(3-메톡시-3-옥소프로필)주석-1, 3-디티올-2-일리덴말로네이트의 제조Preparation of Di (3-methoxy-3-oxopropyl) tin-1, 3-dithiol-2-ylidenemalonate
디(3-메톡시-3-옥소프로필)주석클로라이드와 K2(O2C)C=C(SCH)2·C2H5OH를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 83%의 수율로 얻어진다.When di (3-methoxy-3-oxopropyl) tin chloride and K 2 (O 2 C) C = C (SCH) 2 C 2 H 5 OH were synthesized in the same manner as in Example 4, a white solid was obtained. Obtained in 83% yield.
녹는점 : 66±1℃.Melting Point: 66 ± 1 ℃.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.5-2.0(m, 4H), 2.7-3.1(t, 4H), 3.7(s, 6H), 7.1(s, 2H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 1.5-2.0 (m, 4H), 2.7-3.1 (t, 4H), 3.7 (s, 6H), 7.1 (s, 2H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1562.Infrared spectrum (KBr, cm −1 ): ν (CO), 1562.
[실시예 25]Example 25
디스(트리페닐주석)-1, 3-디티에탄-2-일리덴말로네이트의 제조Preparation of Dis (triphenyltin) -1,3-dithiethane-2-ylidenemalonate
트리페닐주석클로라이드와 K2(O2C)C=C(S)2CH2·H2O를 실시예 10에서와 같은 방법으로 합성하면 흰색의 고체가 84%의 수율로 얻어진다.When triphenyltin chloride and K 2 (O 2 C) C═C (S) 2 CH 2 · H 2 O were synthesized in the same manner as in Example 10, a white solid was obtained in a yield of 84%.
녹는점 :114±2℃.Melting Point: 114 ± 2 ℃.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 3.8(s, 2H), 7.2-7.8(m, 30H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 3.8 (s, 2H), 7.2-7.8 (m, 30H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1611.Infrared spectrum (KBr, cm −1 ): ν (CO), 1611.
[실시예 26]Example 26
디스(트리-n-부틸주석)-1, 3-디티에탄-2-일리덴말로네이트의 제조Preparation of Dis (tri-n-butyltin) -1,3-dithiethane-2-ylidenemalonate
트리-n-부틸주석클로라이드와 K2(O2C)C=C(S)2CH2·H2O를 실시예 1에서와 같은 방법으로 합성하면 엷은 노랑색의 고체가 89%의 수율로 얻어진다.Tri-n-butyltin chloride and K 2 (O 2 C) C = C (S) 2 CH 2 H 2 O were synthesized in the same manner as in Example 1 to obtain a pale yellow solid in 89% yield. Lose.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 0.7-1.9(m, 54H), 3.8(s, 2H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 0.7-1.9 (m, 54H), 3.8 (s, 2H).
적외선스펙트럼(KBr, cm-1)ν(C-O), 1578.Infrared spectrum (KBr, cm −1 ) ν (CO), 1578.
[실시예 27]Example 27
디페닐주석-1, 3-디티에탄-2-일리덴말로네이트의 제조Preparation of diphenyltin-1, 3-dithiethane-2-ylidenemalonate
디페닐주석클로라이드와 K2(O2C)C=C(S)2CH2·H2O를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 85%의 수율로 얻어진다.Diphenyltin chloride and K 2 (O 2 C) C═C (S) 2 CH 2 · H 2 O were synthesized in the same manner as in Example 4 to obtain a white solid in a yield of 85%.
녹는점 : 210℃ 이상.Melting Point: 210 ℃ or higher.
원소분석치(계산치) : C, 45.40(44.09) ; H, 2.53(2.61).Elemental analysis value (calculated): C, 45.40 (44.09); H, 2.53 (2.61).
수소핵자기공명스펙트럼(DMSO-d6), δ(ppm) : 3.8(s, H), 7.3-7.9(m, 10H).Hydrogen nuclear magnetic resonance spectrum (DMSO-d 6 ), δ (ppm): 3.8 (s, H), 7.3-7.9 (m, 10H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1582.Infrared spectrum (KBr, cm −1 ): ν (CO), 1582.
[실시예 28]Example 28
비스(트리페닐주석)이소프로필리덴말로네이트의 제조Preparation of Bis (triphenyltin) isopropylidenemalonate
트리페닐주석클로라이드와 K2(O2C)C=C(CH3)2·2H2O를 실시예 1에서와 같은 방법으로 반응시키면 흰색의 고체가 89%의 수율로 얻어진다. 필요하면 클로로포름-석유에테르 혼합용매하에서 재결정하면 무색의 결정성고체로 얻어진다.When triphenyltin chloride was reacted with K 2 (O 2 C) C = C (CH 3 ) 2 .2H 2 O in the same manner as in Example 1, a white solid was obtained in a yield of 89%. If necessary, recrystallization in a chloroform-petroleum ether mixed solvent gives a colorless crystalline solid.
녹는점 : 146℃.Melting point: 146 ° C.
원소분석치(계산치) : C, 59.20(59.90) ; H, 4.18(4.36).Elemental analysis value (calculated): C, 59.20 (59.90); H, 4.18 (4.36).
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 2.0(s,6H), 7.2-7.8(m,30H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 2.0 (s, 6H), 7.2-7.8 (m, 30H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1644.IR spectrum (KBr, cm -1): ν (CO), 1644.
[실시예 29]Example 29
디페닐주석 이소프로필리덴말로네이트의 제조Preparation of Diphenyl Tin Isopropylidene Malonate
디페닐주석클로라이드와 K2(O2C)C=C(CH3)2·2H2O를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 88%의 수율로 얻어진다.Diphenyltin chloride and K 2 (O 2 C) C = C (CH 3 ) 2 .2H 2 O were synthesized in the same manner as in Example 4 to obtain a white solid in a yield of 88%.
녹는점 : 205.5±0.5℃Melting Point: 205.5 ± 0.5 ℃
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 2.0(s, 6H), 7.2-7.9(m, 10H).Hydrogen nuclear magnetic resonance spectrum (CDCl 3 ), δ (ppm): 2.0 (s, 6H), 7.2-7.9 (m, 10H).
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1644.Infrared spectrum (KBr, cm −1 ): ν (CO), 1644.
[실시예 30]Example 30
디(3-메톡시-3-옥소프로필)주석 이소프로필리덴말로네이트의 제조Preparation of Di (3-methoxy-3-oxopropyl) tin isopropylidenemalonate
디(3-메톡시-3-옥소프로필)주석클로라이드와 K2(O2C)C=C(CH3)2·2H2O를 실시예 4에서와 같은 방법으로 합성하면 흰색의 고체가 90%의 수율로 얻어진다.Di (3-methoxy-3-oxopropyl) tinchloride and K 2 (O 2 C) C = C (CH 3 ) 2 .2H 2 O were synthesized in the same manner as in Example 4 to obtain a white solid. Obtained in% yield.
녹는점 : 58℃.Melting point: 58 ° C.
수소핵자기공명스펙트럼(CDCl3), δ(ppm) : 1.8(t, 4H), 2.0(s, 6H), 2.8(t, 4H), 3.7(s, 6H)Hydrogen Nuclear Magnetic Resonance Spectrum (CDCl 3 ), δ (ppm): 1.8 (t, 4H), 2.0 (s, 6H), 2.8 (t, 4H), 3.7 (s, 6H)
적외선스펙트럼(KBr, cm-1) : ν(C-O), 1577.Infrared spectrum (KBr, cm −1 ): ν (CO), 1577.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019920006404A KR950001702B1 (en) | 1992-04-16 | 1992-04-16 | Organotinmalonates derivatives, and process for their preparation |
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| KR1019920006404A KR950001702B1 (en) | 1992-04-16 | 1992-04-16 | Organotinmalonates derivatives, and process for their preparation |
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| Publication Number | Publication Date |
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| KR930021648A KR930021648A (en) | 1993-11-22 |
| KR950001702B1 true KR950001702B1 (en) | 1995-02-28 |
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