CN1110476C - β-氨基乙烯基酮在制备β-二酮中的用途 - Google Patents
β-氨基乙烯基酮在制备β-二酮中的用途 Download PDFInfo
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- 229910052783 alkali metal Inorganic materials 0.000 description 5
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
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- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KJGMCIWRNDQSCC-UHFFFAOYSA-N 1,5-diaminopentan-3-one Chemical compound NCCC(=O)CCN KJGMCIWRNDQSCC-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N 2-butanol Substances CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- PXKOUGPWVWRTQH-UHFFFAOYSA-N 3-amino-1-cyclopropyl-3-(3,4-dibromo-2-methylsulfanylphenyl)prop-2-en-1-one Chemical compound CSC1=C(Br)C(Br)=CC=C1C(N)=CC(=O)C1CC1 PXKOUGPWVWRTQH-UHFFFAOYSA-N 0.000 description 1
- XRGNNGKMBMRDJE-UHFFFAOYSA-N 3-amino-1-cyclopropyl-3-(3,4-dichloro-2-methylsulfanylphenyl)prop-2-en-1-one Chemical compound CSC1=C(Cl)C(Cl)=CC=C1C(N)=CC(=O)C1CC1 XRGNNGKMBMRDJE-UHFFFAOYSA-N 0.000 description 1
- KAQXSEXZAKRKHC-UHFFFAOYSA-N 3-amino-1-cyclopropyl-3-[2-methylsulfanyl-4-(trifluoromethyl)phenyl]prop-2-en-1-one Chemical compound CSC1=CC(C(F)(F)F)=CC=C1C(N)=CC(=O)C1CC1 KAQXSEXZAKRKHC-UHFFFAOYSA-N 0.000 description 1
- ULZKKHZIZZIFBD-UHFFFAOYSA-N 3-amino-3-(4-bromo-2-methylsulfanylphenyl)-1-cyclopropylprop-2-en-1-one Chemical compound CSC1=CC(Br)=CC=C1C(N)=CC(=O)C1CC1 ULZKKHZIZZIFBD-UHFFFAOYSA-N 0.000 description 1
- BOEXRSBRHUASIJ-UHFFFAOYSA-N 3-amino-3-(4-bromo-3-chloro-2-methylsulfanylphenyl)-1-cyclopropylprop-2-en-1-one Chemical compound CSC1=C(Cl)C(Br)=CC=C1C(N)=CC(=O)C1CC1 BOEXRSBRHUASIJ-UHFFFAOYSA-N 0.000 description 1
- VNILUFDSGYNGIW-UHFFFAOYSA-N 3-amino-3-(4-chloro-2-methylsulfanylphenyl)-1-cyclopropylprop-2-en-1-one Chemical compound CSC1=CC(Cl)=CC=C1C(N)=CC(=O)C1CC1 VNILUFDSGYNGIW-UHFFFAOYSA-N 0.000 description 1
- ZRTRKOVOTGELGQ-UHFFFAOYSA-N 3-amino-3-(4-chloro-3-ethoxy-2-methylsulfanylphenyl)-1-cyclopropylprop-2-en-1-one Chemical compound CCOC1=C(Cl)C=CC(C(N)=CC(=O)C2CC2)=C1SC ZRTRKOVOTGELGQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- 229930194542 Keto Natural products 0.000 description 1
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-L methyl phosphate(2-) Chemical compound COP([O-])([O-])=O CAAULPUQFIIOTL-UHFFFAOYSA-L 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- LZTRCELOJRDYMQ-UHFFFAOYSA-N triphenylmethanol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C1=CC=CC=C1 LZTRCELOJRDYMQ-UHFFFAOYSA-N 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/32—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to an acyclic carbon atom of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Steroid Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及新颖的通式(VI)的β-氨基乙烯基酮其中R1为烯基、炔基、环烷基或环烯基;R2为吸电子基团,如硝基、酰基、酯基、烷基硫代、氨基甲酰基、硫代氨基甲酰基或卤代烷基;R3为烷基、烷氧基或卤素原子;n为1或2而m为0,1,2或3。本文叙述了在强碱存在下通过使被(R2)n和任选的(R3)m取代的苄腈与酮类R1-CO-CH2间进行缩合反应来制备这些化合物的方法,以及使用所述的通式(VI)的β-氨基乙烯基酮来制备相应的二酮的方法。
Description
本发明是申请号为94192585专利申请的分案申请。
本发明涉及在与氨基相连的碳原子上具有芳香取代基的新的β-氨基乙烯基酮在制备β-二酮中的用途。
芳香二酮的通式为:其中X表示脂族或环脂族基团,而Y表示芳香族基团。它作为中间体用于通式(II)的4-苯甲酰基异噁唑的衍生物的合成。(II)为广谱除莠剂,这是现有技术中公知的(参见EP-A-0,418,175)。
从结构式(I)的二酮来合成4-苯甲酰基异噁唑是通过如下两个阶段连接完成的:
-使式(I)的二酮与三烷基原甲酸酯或二甲基甲酰胺二烷基乙缩醛反应产生相应的通式为(III)的产物:其中L为O-烷基或N,N-二烷氨基;此反应一般在惰性溶剂,如乙醚或四氢呋喃等中完成,温度范围为从0℃到混合物的回流温度;和
-式(III)化合物与羟基胺盐的反应。此反应一般在乙醇或乙腈等溶剂中,任意地有碱或酸接受物(如三乙胺或醋酸钠等)存在下完成。
对于合成起始物式(I)的β-二酮,则常由如下三个阶段连接完成:
一-使通式(IV)芳香腈进行水解反应,得到一相应的羧酸;
Y-CN (IV)
-脂肪醇,如甲醇等,衍生化反应剂制成此羧酸的酯;以及
-使所述的酯与通式(V)的酮进行缩合反应。该反应在强碱存在时及与Claisem缩合反应一致的条件下完成。
本发明的主要目的为:
-提供从芳香腈开始,得到作为中间体用于4-苯甲酰基异噁唑衍生物的合成的β-二酮的途径。
-具有很多优点:步骤少,产率高,及易进行工业化生产。
根据这个途径,可以制备与氨基相连的碳原子上具有芳香取代基的β-氨基乙烯基酮,它具有双重特征:一方面它是全新的化合物,另一方面用转换反应可以很容易地转换为所需的β-二酮,可以在制备的反应混合物中分离得到氨基乙烯基酮或直接制得含有氨基乙烯基酮的反应混合物。
I-在第一主题中,本发明涉及通式(VI)的β-氨基乙烯基酮。
其中,
-R1表示任意被一个或几个R4或OR4基团取代的、含有3-6个碳原子的环烷基;
-R2表示SR4烷基硫代,或具有直至4个碳原子的直链或支链卤代烷基或卤代烷氧基,其中卤代是单卤代到完全卤代;
-R3表示含最多为4个碳原子的直链或支链烷基或烷氧基,或是一个卤素原子;
-R4表示含最多为4个碳原子的直链或支链烷基。
值得一提的是:更优选的β-氨基乙烯基酮化合物是式(VI)中:
-n表示1或2,m为0-2的整数,附加条件为m+n不得超过3;
-(R2)n表示的基团在苯环的2-位,而(R2)n和/或(R3)m表示的其它基团在苯环的3-和/或4-位上。
值得一提的是:作为式(VI)化合物β-氨基乙烯酮特定代表属于在前文更优选化合物中已确定的,其中:
-R1表示环丙基或1-甲基环而基;
-R2表示甲基硫代或乙基硫代或三氟甲基或三氟甲氧基;
-R3表示甲基、乙基、甲氧基或乙氧基或氯、溴或碘原子。
特别值得一提的是:作为β-氨基乙烯基酮的一些特殊例子,有下列一些化合物。
1.1-氨基-3-环丙基-1-(2-甲基硫代-4-氯苯基)-1-丙烯-3-酮;
2.1-氨基-3-环丙基-1-(2-甲基硫代-4-三氟甲苯基)-1-丙烯-3-酮;
3.1-氨基-3-环丙基-1-(2-甲基硫代-4-溴苯基)-1-丙烯-3-酮;
4.1-氨基-3-环丙基-1-(2-甲基硫代-3,4-二氯苯基)-1-丙烯-3-酮;
5.1-氨基-3-环丙基-1-(2-甲基-4-甲基硫代)-1-丙烯-3-酮;
6.1-氨基-3-环丙基-1-(2-甲基硫代-3-氯-4-溴苯基)-1-丙烯-3-酮;
7.1-氨基-3-环丙基-1-(2-甲基硫代-3-乙氧基-4-氯苯基)-1-丙烯-3-酮;
8.1-氨基-3-环丙基-1-(2-甲基硫代-3,4-二溴代苯基)-1-丙烯-3-酮;
II-在第二主题中,本发明涉及了制备式(VI)的β-氨基乙烯基酮或基于氨基乙烯基酮的混台物的方法,其特征在于它包括使1-4摩尔的下式(VII)的甲基有机酮:其中R1的定义与权利要求1-3的式(VI)中所述的相同,与1摩尔下式(VIII)的芳香腈进行缩台反应,
其中R2,R3,n和m的含义与式(VI)中的相同,所述的缩合反应在惰性气氛下、用较长时间的加热、在惰性溶剂介质中、在1-4摩尔强碱存在下进行,所述的惰性溶剂介质选自与水不相混溶的非质子传递的极性溶剂的惰性溶剂或惰性溶剂的混合物,所述的强碱选自:
(i)衍生自碱金属和一元伯醇的醇盐,在其结构中,与CH2OH基团相连的残基是支链基团,所述的支链基团中直接与CH2OH基团相连的碳原子本身连有2个或3个其它碳原子,这些其它碳原子属于相同或不同的基团,所述的基团各自选自有直至3个碳原子的直链或支链烷基和苯基基团的基团;
(ii)衍生自碱金属和二级或三级一元醇的醇盐,对于二级醇来说,有两个相同或不同的基团与CHOH相连,对于三级醇,有三个相同或不同的基团与COH相连,这些基团选自具有最多为4个碳原子的直链或支链烷基和苯基的基团;和
(iii)(i)或(ii)的醇盐在一元醇中的溶液,所述的一元醇是制备(i)或(ii)中醇盐的一元醇,
以氨基乙烯基酮为主的混合物中,除化台物VI以外,特别含有通式如下的嘧啶:其中Ar是相同的。由下式表示:
R1的定义与式(VI)中所叙的相同,
对于化合物IX有如下的附加说明:
*(a)当n=0和m=0或(b)当n=0和m=1或2,及R3表示烷基或烷氧基或卤素时,在(a)或(b)中的R1不能是烷基,也不能是结构式(R5-)p-苯基(-CR6R7)q-,此处q=0;
*(c)当n=1和m=0及R2表示NO2时,R1不能为(R5-)p-苯基(-CR6R7)q-基团,此处q=0。
一般需用轻微正压的惰性气体,如氮气或氩气,且在惰性溶剂或惰性溶剂混合物中完成缩台反应。
优选溶剂为与水不相混溶的非质子传递极性溶剂,如四氢呋喃、二恶烷、乙醚、甲基叔丁基醚、苯、氯苯或甲苯。
反应的温度为30℃到120℃,较好地在上述范围内选择能使反应混合液回流的温度。
反应时间根据所选择的反应温度的不同而不同,例如,从30分钟到5小时不等。
反应物各组分的摩尔比为:
-式(VIII)的芳香腈: 1摩尔
-式(VII)的R1甲基酮: 1到4摩尔,较好为1.3摩尔到2摩尔。
-醇盐:1-4摩尔,较好为1.3-2摩尔。
作为强碱使用的醇盐是衍生自下列醇类醇钠盐或醇钾盐:
*异丁醇(CH3)2CH-CH2OH
*异丙醇(CH3)2-CHOH
*仲丁醇CH3(C2H5)CHOH
*叔丁醇(CH3)3C-COH
*二甲基苯甲醇(CH3)2(C6H5)-COH
*三苯基甲醇(C6H5)3-COH
或者是在上述醇中的醇盐溶液。
在选自下列组中的强碱存在下的缩合反应能得到最好的结果:
(iv)衍生自碱金属和三级一元醇的醇盐,在其结构中,与COH相连的3个相同或不同的基团选自有1或2个碳原子的直链烷基和苯基,
(v)(iv)的醇盐在一元醇中的溶液,所述的一元醇是制备(iv)中醇盐的一元醇。
醇盐可从不同途径来制备,通过将碱金属溶于相应的醇中可制得醇盐;也可用碱金属甲醇盐与相应醇反应制备,另一种制备方法是用碱金属氢化物与相应的醇反应。可在缩合反应的介质外或任选地在反应介质中制得醇盐。该制备一般通过本身已知的方法进行;用1-5摩尔,较好为1.1-4摩尔相应的醇与1摩尔的碱试剂反应物(碱金属,碱金属甲醇盐和碱金属氢化物)反应。所形成的醇盐可以以纯状态或在醇过量时存在于反应的醇中的溶液形式使用。在本说明书中,术语“一元醇中的醇盐溶液”可理解为每1摩尔强碱盐中含有最多为4摩尔的醇,最好为0.1-3摩尔。
当所有的式VIII腈反应完全后,中止反应的一个方法为冷却反应混合物,通过加入预定量的无机含氧酸或氢酸调节pH值到中性,并加入足量的水溶解生成的盐;最好以酸的稀水溶液形式一起加入酸和水。
当缩合反应在水不相混溶的溶剂介质中进行时,按前叙的处理方法能得到一个水/有机二相混合物,可以如通过放置,然后浓缩除去溶剂分离含有生成氨基乙烯基酮的有机相。
除去溶剂后主要得到式(VI)的β-氨基乙烯基酮的残留物,此处表述“主要得到”为的是强调在这种情况下,残留的混合产物中除β-氨基乙烯基酮外,尚存有少量下列副产物:
*一般通式如下的嘧啶:
*和/或通式如下的酰胺:此处Ar互相相同,表示:此处R1有一般或较好的限定,在前面通式(VI)的氨基乙烯酮中己显示。
在本说明书中,“基于氨基乙烯酮的混合物”的表达是指含有下列混合物的残留物:式(VI)的β-氨基乙烯基酮及少量式(IX)和/或(X)的副产物混合物中副产物的量基于氨基乙烯基的量以摩尔%表示,不超过:
-嘧啶(IX):14%
-酰胺(X):35%。
当残留物是以氨基乙烯基酮为主要产物的混合物形式存在时,通过用适当的溶剂,例如甲苯或甲苯/环己烷混合溶剂重结晶混合物,可以得到纯的β-氨基乙烯基酮。
当缩合反应是在水不相混溶的溶剂介质中进行时,任意地在除去原有所有或部分溶剂后,经加入酸和水,以及适当的第三种溶剂进行萃取操作,可以分离得到β-氨基酮或氨基乙基酮为主要成分的混合物。
III-第三主题,本发明涉及式(VI)β-氨基乙烯基酮或基于氨基乙烯基酮的混合物在制备通式(XI)的β-二酮中的应用:其中R1、R2、R3,n和m为前面相关结构式(VI)中的普通或特定的一种限制。所述的用途的特征在于它包括了使式(VI)β-氨基乙烯基酾或基于氨基乙烯基酮的混合物进行水解反应,水解反应在水和强的无机或有机酸存在下,任意地是在惰性溶剂中进行。
水解反应可以无溶剂进行或在惰性溶剂或惰性溶剂混合物加入到起始反应物中的溶剂介质中进行。
当水解反应是在与本发明第二主题等同的溶剂中进行时,特别是溶剂不仅等同且又是极性非质子传递的及不相溶于水时,溶剂的使用是有利的。一个更理想的方法是在使用β-氨基乙烯基酮或以氨基乙烯基酮为主的混合物时获得有机相,它是通过本发明第二主题中反应混合物的处理方法,再从水/有机二相中分出水相而得到的。本方法因将缩合反应(本发明第二主题)和水解反应(本发明第三主题)连在一起,而使得反应在同一设备中,缩合反应后无需分离β-氨基乙烯基酮,也不必根本改变反应混合物的组成而从缩合反应转到水解反应,而更显其优越性。
水解反应的温度范围从40℃到120℃,当水解反应在溶剂中进行时,温度选择较好地在对应于反应混合物的回流温度的上述范围里。
反应时间因温度不同而不同,台30分钟至5小时之间。
反应在下列各组分配比下较为有利:
-式VI的β-氨基乙烯酮: 1摩尔,
-水:1-20摩尔,较好在1.5-10摩尔,
-强酸:1-6H+离子,较好为1.1-4H+离子。
强的无机和有机酸可理解为任意地含氧原子的单元或多元酸,它至少含有一个酸基团(当有几个酸基团时),在水中的电离常数pKa不大于3。值得一提的是,无机酸中的这一类酸为盐酸、硫酸、(正)磷酸、焦磷酸、值得一提的是,有机酸为:有机磺酸,特别是对甲苯磺酸,甲磺酸和萘磺酸;有机磷酸,特别是单烷基可单苯环基磷酸,如甲基磷酸或苯基磷酸;或强的卤代多元羧酸如二卤代或三卤代(尤其是氯和氟)乙酸或丙酸。本发明中,优先使用的强酸为任意地含氧的无机一元酸或多元酸,最多使用盐酸和硫酸。
对于反应中需用的水和强酸,有利的是以酸性水溶液的形式一起加入混合物中,浓度和量取决于水的量以及所需的H+离子浓度。
当所有的β-氨基乙烯基酮反应完全后,冷却反应混合物来中止反应,按已知的方法进行处理,以便从中分离出式(XI)的β-二酮。
例如,当水解反应在水不相混溶的溶剂介质中进行时,得到水/有机二相的反应混合物,如通过放置分离含有形成的B-二酮的有机相,浓缩所得的有机相以除去反应溶剂。
当主要为氨基乙烯基酮的混合物作为起始物进行水解时,作了β-二酮外可以最后的有机相中了现,上述的嘧啶和/或酰胺副产物。
除除去溶剂后,若有必要,可对所得到的β-二酮用已知的方法重结晶来进行纯化。
下叙实施例说明本发明并展示如何付之实际,但并不用来限制本发明。
实施例1
根据本发明第二主题的方法制备β-氨基乙烯基酮的实例
所用的设备为装有温度计、垂直接口的回流冷凝器、加热系统、搅拌系统和用来通入氩气达稍正压力状态的系统。
在室温(25℃)下依次向反应器中加入下列物质:-10.9克(0.050摩尔)1-氰基-2-甲基硫代-4-三氟甲基苯-50cm3甲基叔丁基醚-7.2g(0.075摩尔)纯态的叔丁醇钠。
该混合物在回流(57℃)下搅拌加热3小时30分钟。
冷却到室温后,向反应混合物中加入25cm3 1N HCl水溶液,这使pH至中和值,得到水/有机二相混合物。
分离水相和有机相,然后中用25cm3水萃取有机相,用减压蒸馏除去溶剂进行浓缩。残留产物以高效液相色谱分析,分析结果如下:
1)开始物腈转化的程度(摩尔)为100%
2)形成如下三个化合物的混合物
2.1.β-氨基乙烯基酮,式为:环丙基
按反应物腈计算,其摩尔产率为92%。
2.3.胺,式为:其中Ar为
按反应腈计算,其摩尔产率为4%。
纯品β-氨基乙烯基酮可以通过在上述反应混合物中加入50cm3的甲苯重结晶而获得。NMR和IR分析及质谱都证明了如上所述的结构。
-NMR(1H,CDCl3):0.75-0.98ppm(m,4H),1.71ppm(m,3H),2.44ppm(s,3H),5.0ppm(s,1H),5:28ppm(s,1H),7.38ppm(m,3H)9,65ppm(s,1H);
-IR光谱:3413-3254cm-1(NH2),1613cm-1(C=O)1320-1140cm-1(CF3),2924cm-1(SCH3);
-质谱(仪器:VG ZAB 2SF;光源:EICI;M/△M=2000):M=301g。
实施例2
使用第三主题中发明条件来制备β-二酮的例子。
设备与实施例1中所述的相同。
实施例中得到水/有机二相混合物,从留在反应容器内的有机相中分离出水相,此时本阶段结束。得到含2.1,2.2,2.3三个化合物的有机相,这在实施例1中已叙述。
将10cm3 10N硫酸水溶液加入有机相中,在60℃下加热搅拌3小时,一个新的水/有机双相就形成了。
最后,冷却至室温(25℃)后,两相分离、有机相用每升含5克碳酸氢盐的NaHCO3水溶液20CM3萃取,再用20cm3水萃取。除去有机相的溶剂,得到的残留物用210cm3的甲醇重结晶,就得到了β-二酮纯品,结构式为:NMR和质谱分析,结果与上述结构一致:
-NMR(1H,CDCl3):二醇式(90mol%):0.96-1.17ppm(mn,4H),109ppm(m,1H),2.45ppm(s,3H),6.03ppm(s,1H为=CH-CO).7.35-7.56ppm(m,3H),>11ppm(s,1H);
*酮式(100mol%):4.2ppm(s,2H为CO-CH2-CO);
-质谱:M=302g;
-进一步的说明:m.p.(熔点)=60℃。
Claims (6)
1.一种下式(VI)β-氨基乙烯基酮在制备下式(XI)的β-二酮中的用途:
其中,
-R1表示任意被一个或几个R4或OR4基团取代的、含有3-6个碳原子的环烷基;
-R2表示SR4烷基硫代,或具有直至4个碳原子的直链或支链卤代烷基或卤代烷氧基,其中卤代是单卤代到完全卤代;
-R3表示含最多为4个碳原子的直链或支链烷基或烷氧基,或是一个卤素原子;
-R4表示含最多为4个碳原子的直链或支链烷基;
n表示1或2,m为0-2的整数,附加条件为m+n不得超过3;
其中R1、R2、R3、n和m的定义同上,
其特征在于,使结构式(VI)的β-氨基乙烯酮进行水解反应,此水解反应在水及强酸存在下发生的,所述的强酸在水中离子浓度的pKa小于或等于3。
2.根据权利要求1所述的用途,其中所述的水解反应在惰性溶剂介质中进行。
3.根据权利要求1所述的用途,其特征在于水解反应溶剂介质为选自水不相混溶的非质子传递的极性溶剂的惰性溶剂或惰性溶剂混合物。
4.根据权利要求1或2所述的用途,其特征在于该反应具有如下组分的比例:
-式VI的β-氨基乙烯基酮:1摩尔
-水:1-20摩尔
-强酸:1-6H+离子。
5.根据权利要求1所述的用途,其中所述的强酸选自无机酸、有机磺酸、有机磷酸和卤代羧酸。
6.根据权利要求1所述的用途,其特征在于水解反应的温度范围在40℃-120℃。
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FR07867/1993 | 1993-06-23 | ||
FR07867/93 | 1993-06-23 | ||
FR9307867A FR2706893B1 (zh) | 1993-06-23 | 1993-06-23 |
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CN94192585A Division CN1043229C (zh) | 1993-06-23 | 1994-06-16 | β-氨基乙烯基酮及其制备方法 |
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CN94192585A Expired - Fee Related CN1043229C (zh) | 1993-06-23 | 1994-06-16 | β-氨基乙烯基酮及其制备方法 |
CN98118643A Expired - Fee Related CN1110476C (zh) | 1993-06-23 | 1998-08-21 | β-氨基乙烯基酮在制备β-二酮中的用途 |
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EP (1) | EP0705243B1 (zh) |
JP (1) | JPH08511792A (zh) |
KR (1) | KR960703111A (zh) |
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AT (1) | ATE167671T1 (zh) |
AU (1) | AU675338B2 (zh) |
BR (1) | BR9407271A (zh) |
CA (1) | CA2165688A1 (zh) |
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FI (1) | FI956230A (zh) |
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WO1998055446A1 (en) * | 1997-06-03 | 1998-12-10 | Eastman Chemical Company | Process for the preparation of thioether-substituted aromatic ketones |
US6143935A (en) * | 1997-06-03 | 2000-11-07 | Eastman Chemical Company | Process for the preparation of 1,3-dicarbonyl compounds |
GB9714306D0 (en) | 1997-07-07 | 1997-09-10 | Rhone Poulenc Agrochimie | New processes |
GB9714305D0 (en) | 1997-07-07 | 1997-09-10 | Rhone Poulenc Agrochimie | Chemical process |
US6096929A (en) * | 1998-06-02 | 2000-08-01 | Eastman Kodak Company | Process for the preparation of thioether-substituted aromatic ketones |
US6337418B1 (en) | 1999-04-09 | 2002-01-08 | Eastman Chemical Co. | Preparation of C1-C5 alkyl esters of nitro or thioether substituted aromatic carboxylic acids |
CN113004179B (zh) * | 2019-12-20 | 2022-06-24 | 江苏中旗科技股份有限公司 | 一种异噁唑草酮关键中间体的制备方法 |
CN115925583A (zh) * | 2022-10-31 | 2023-04-07 | 南京工业大学 | 一种β-氟烷基-β-氨基乙烯基酮化合物的制备方法 |
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EP0487870A2 (en) * | 1990-11-30 | 1992-06-03 | American Cyanamid Company | Insecticidal and acaricidal diarylpyrrolecarbonitrile and diarylnitropyrrole compounds |
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1993
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- 1994-06-20 ZA ZA944367A patent/ZA944367B/xx unknown
- 1994-06-22 TW TW083105648A patent/TW307750B/zh active
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EP0487870A2 (en) * | 1990-11-30 | 1992-06-03 | American Cyanamid Company | Insecticidal and acaricidal diarylpyrrolecarbonitrile and diarylnitropyrrole compounds |
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Publication number | Publication date |
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KR960703111A (ko) | 1996-06-19 |
CN1125940A (zh) | 1996-07-03 |
FR2706893A1 (zh) | 1994-12-30 |
US5684206A (en) | 1997-11-04 |
HU9503774D0 (en) | 1996-02-28 |
AU7076794A (en) | 1995-01-17 |
JPH08511792A (ja) | 1996-12-10 |
ATE167671T1 (de) | 1998-07-15 |
DK0705243T3 (da) | 1998-11-09 |
EP0705243A1 (fr) | 1996-04-10 |
FR2706893B1 (zh) | 1995-08-04 |
DE69411274T2 (de) | 1998-12-24 |
HRP940364B1 (en) | 1998-12-31 |
BR9407271A (pt) | 1996-10-01 |
TR28485A (tr) | 1996-09-10 |
WO1995000476A1 (fr) | 1995-01-05 |
ES2117791T3 (es) | 1998-08-16 |
CZ289727B6 (cs) | 2002-03-13 |
EP0705243B1 (fr) | 1998-06-24 |
ZA944367B (en) | 1995-12-20 |
HU215547B (hu) | 1999-01-28 |
TW307750B (zh) | 1997-06-11 |
CZ341795A3 (en) | 1996-04-17 |
HRP940364A2 (en) | 1996-08-31 |
FI956230A0 (fi) | 1995-12-22 |
DE69411274D1 (de) | 1998-07-30 |
IL110067A (en) | 1998-04-05 |
AU675338B2 (en) | 1997-01-30 |
HUT73648A (en) | 1996-09-30 |
IL110067A0 (en) | 1994-10-07 |
CA2165688A1 (fr) | 1995-01-05 |
FI956230A (fi) | 1995-12-22 |
CN1043229C (zh) | 1999-05-05 |
CN1215047A (zh) | 1999-04-28 |
RU2131413C1 (ru) | 1999-06-10 |
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