CN103664625A - 2,3,4,6-tetrasubstituted phenol derivative and preparation method thereof - Google Patents
2,3,4,6-tetrasubstituted phenol derivative and preparation method thereof Download PDFInfo
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- -1 2,3,4,6-tetrasubstituted phenol Chemical class 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 150000002170 ethers Chemical class 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 150000002505 iron Chemical class 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 10
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 40
- 150000007529 inorganic bases Chemical class 0.000 description 29
- 239000002904 solvent Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 159000000014 iron salts Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 2
- ITQWCCLRNKNTTP-BMRADRMJSA-N ethyl (2E)-2-(phenoxymethylidene)-4-phenylbut-3-ynoate Chemical compound C=1C=CC=CC=1C#C/C(C(=O)OCC)=C\OC1=CC=CC=C1 ITQWCCLRNKNTTP-BMRADRMJSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- KKAHGSQLSTUDAV-UHFFFAOYSA-M 3-butynoate Chemical compound [O-]C(=O)CC#C KKAHGSQLSTUDAV-UHFFFAOYSA-M 0.000 description 1
- 0 Cc1c(-c2ccccc2)c(O)c(*)cc1C=O Chemical compound Cc1c(-c2ccccc2)c(O)c(*)cc1C=O 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZTICSVKGPFWKSS-OBGWFSINSA-N ethyl (2E)-4-(4-methylphenyl)-2-(phenoxymethylidene)but-3-ynoate Chemical compound CCOC(=O)C(=C\Oc1ccccc1)\C#Cc1ccc(C)cc1 ZTICSVKGPFWKSS-OBGWFSINSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ATHHXGZTWNVVOU-UHFFFAOYSA-N monomethyl-formamide Natural products CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种2，3，4，6-四取代苯酚类衍生物，其结构如式(I)所示。本发明还公开了2，3，4，6-四取代苯酚类衍生物的制备方法，在室温和氮气保护下，以烯炔醚类化合物和1，3-二羰基类化合物为原料，以铁盐为催化剂、在存在碱的条件下，合成所述2，3，4，6-四取代苯酚类衍生物。本发明制备方法具有低成本、反应条件温和、对环境友好等有益效果。The invention discloses a 2,3,4,6-tetrasubstituted phenol derivative, the structure of which is shown in formula (I). The invention also discloses a preparation method of 2,3,4,6-tetrasubstituted phenol derivatives. Under room temperature and nitrogen protection, enyne ether compounds and 1,3-dicarbonyl compounds are used as raw materials, and iron The salt is used as a catalyst, and the 2,3,4,6-tetrasubstituted phenol derivatives are synthesized in the presence of a base. The preparation method of the invention has beneficial effects such as low cost, mild reaction conditions, and environmental friendliness.
Description
技术领域 technical field
本发明属有机化合物及合成的技术领域，具体地涉及一种2，3，4，6-四取代苯酚类衍生物及其合成制备方法。 The invention belongs to the technical field of organic compounds and synthesis, and in particular relates to a 2,3,4,6-tetrasubstituted phenol derivative and a synthesis preparation method thereof. the
背景技术 Background technique
多取代苯酚类衍生物(phenol)是一类重要的芳香类化合物。这类化合物广泛应用于塑料、医药、农药、香料、染料以及涂料等方面，此外，还可用作杀菌剂、防腐剂等。关于2，3，4，6-四取代苯酚类衍生物的合成已有文献报道，但是这类报道目前还很少，且使用昂贵的金属催化剂如钯、铑等，而且报道的方法局限性在于：(1)采用了昂贵的金属试剂，增加了反应成本；(2)钯、铑等金属具有一定的毒性，易造成环境污染。利用钯、铑、钛等金属催化的2，3，4，6-四取代苯酚类衍生物合成方法已有相关报道，例如：文献(1)Didier，C.；Alain，D.Tetrahedron Lett.1997，38，1397-1398.(2)Gopal，B.；Van T.H.N.；Ehsan U.；Sunanda L.；Helmar G.；Peter L.J.Org.Chem.2004，69，9128-9134.(3)Gerson，M.；Simone，L.；Helmut，R.；Anke，S.；Christine，F.；Peter，L.Synthesis2009，13，2236-2248.(4)Mohanad，S.；Abdolmajid，R.；Olumide，F.；Ibrar H.；Mirza，A.Y.；M.L.；Stefanie，R.；Helmut，R.；Christine，F.；Peter，L.Org.Biomol.Chem.2009，7，2182-2186.。 Multi-substituted phenol derivatives (phenol) is an important class of aromatic compounds. These compounds are widely used in plastics, medicines, pesticides, spices, dyes, and coatings. In addition, they can also be used as fungicides, preservatives, etc. There are existing literature reports on the synthesis of 2,3,4,6-tetrasubstituted phenol derivatives, but such reports are still rare at present, and expensive metal catalysts such as palladium, rhodium, etc. are used, and the method limitations of the reports are : (1) expensive metal reagents have been adopted, which increases the reaction cost; (2) metals such as palladium and rhodium have certain toxicity, which easily cause environmental pollution. Utilize palladium, rhodium, titanium and other metal catalyzed 2,3,4,6-tetrasubstituted phenol derivatives synthetic methods have related reports, for example: Document (1) Didier, C.; Alain, D.Tetrahedron Lett.1997 , 38, 1397-1398. (2) Gopal, B.; Van T.H.N.; Ehsan U.; Sunanda L.; .; Simone, L.; Helmut, R.; Anke, S.; Christine, F.; Peter, L. Synthesis 2009, 13, 2236-2248. (4) Mohanad, S.; .; Ibrar H.; Mirza, A.Y.; M.L.; Stefanie, R.; Helmut, R.; Christine, F.; the
现有技术中2，3，4，6-四取代苯酚类衍生物的制备方法中存在以下缺点：采用了昂贵的金属试剂，增加了反应成本；且由于采用的金属具有一定的毒性，易造成环境污染。 In the prior art, there are following disadvantages in the preparation method of 2,3,4,6-tetrasubstituted phenol derivatives: expensive metal reagents are used, which increases the reaction cost; and because the metals used have certain toxicity, it is easy to cause environmental pollution. the
发明内容 Contents of the invention
本发明的目的是提供一种2，3，4，6-四取代苯酚类衍生物。 The object of the present invention is to provide a kind of 2,3,4,6-tetrasubstituted phenol derivatives. the
本发明提供的2，3，4，6-四取代苯酚类衍生物的结构，如以下式(I)所示： The structure of 2,3,4,6-tetrasubstituted phenol derivatives provided by the present invention is as shown in the following formula (I):
其中，R1＝C1-20的烷基、乙氧基；R2为C1-20的烷基；R3为吸电子基、供电子基；其中，吸电子基可以是卤素，供电子基可以是烷基、烷氧基。 Wherein, R 1 =C 1-20 alkyl, ethoxy; R 2 is C 1-20 alkyl; R 3 is an electron-withdrawing group, an electron-donating group; wherein, the electron-withdrawing group can be a halogen, and the electron-donating group The group can be alkyl, alkoxy.
本发明的另一目的是提供一种铁催化的、低成本、反应条件温和、对环境友好的2，3，4，6-四取代苯酚类衍生物的合成方法。 Another object of the present invention is to provide an iron-catalyzed, low-cost, mild reaction condition, and environmentally friendly synthesis method for 2,3,4,6-tetrasubstituted phenol derivatives. the
本发明提供的2，3，4，6-四取代苯酚类衍生物的制备方法，采用以下技术方案：烯炔醚类化 合物和1，3-二羰基类化合物为原料进行环化反应，以铁盐为催化剂，碳酸铯为碱，合成2，3，4，6-四取代苯酚类衍生物。该方法有原料简单易得，后处理简便、催化剂廉价、收率良好和对环境友好的优点。所述方法如以下式(II)所示： The preparation method of 2,3,4,6-tetrasubstituted phenol derivatives provided by the present invention adopts the following technical scheme: enyne ether compounds and 1,3-dicarbonyl compounds are used as raw materials for cyclization reaction, 2,3,4,6-tetrasubstituted phenol derivatives were synthesized with iron salt as catalyst and cesium carbonate as base. The method has the advantages of simple and easy-to-obtain raw materials, convenient post-treatment, cheap catalyst, good yield and environmental friendliness. Described method is as shown in following formula (II):
其中，R1＝C1-20的烷基、乙氧基；R2为C1-20的烷基；R3为吸电子基、供电子基；其中，吸电子基可以是卤素，供电子基可以是烷基、烷氧基。 Wherein, R 1 =C 1-20 alkyl, ethoxy; R 2 is C 1-20 alkyl; R 3 is an electron-withdrawing group, an electron-donating group; wherein, the electron-withdrawing group can be a halogen, and the electron-donating group The group can be alkyl, alkoxy.
本发明提供的2，3，4，6-四取代苯酚类衍生物的合成方法，其具体过程是，在室温和氮气保护下，把烯炔醚类化合物和1，3-二羰基类化合物在催化剂铁盐、无机碱存在下，于适当溶剂中，升温至35℃，反应1-16小时，经分离提纯后，得到多取代苯酚类衍生物，烯炔醚：1，3-二羰基化合物：无机碱：铁盐的摩尔比为1.0：2.0：2.0：0.1，收率50-84％，所述的铁盐为Fe(ClO4)39H2O、Fe(SO4)3、FeCl3等，所述的无机碱为Cs2CO3，所述的溶剂可以是N，N-二甲基甲酰胺(DMF)。 The synthetic method of 2,3,4,6-tetrasubstituted phenol derivatives provided by the present invention, its concrete process is, under room temperature and nitrogen protection, enyne ether compound and 1,3-dicarbonyl compound are in In the presence of catalyst iron salt and inorganic base, heat up to 35°C in an appropriate solvent, react for 1-16 hours, and obtain multi-substituted phenol derivatives after separation and purification, enyne ether: 1,3-dicarbonyl compound: The molar ratio of inorganic base: iron salt is 1.0:2.0:2.0:0.1, and the yield is 50-84%. The said iron salt is Fe(ClO 4 ) 3 9H 2 O, Fe(SO 4 ) 3 , FeCl 3 etc , the inorganic base is Cs 2 CO 3 , and the solvent may be N,N-dimethylformamide (DMF).
与现有技术相比，本发明具有以下优点： Compared with prior art, the present invention has the following advantages:
(1)原料烯炔醚类化合物合成简便，1，3-二羰基类化合物是常见的化工原料。 (1) Raw material enyne ether compounds are easy to synthesize, and 1,3-dicarbonyl compounds are common chemical raw materials. the
(2)所用的铁盐无毒，对环境友好，价格低廉。 (2) The iron salt used is non-toxic, environmentally friendly and cheap. the
(3)采用的无机碱是常见的化工原料，易于获取。 (3) The inorganic base used is a common chemical raw material and is easy to obtain. the
(4)反应条件温和，可以得良好的收率到此类化合物，且产物稳定。 (4) The reaction conditions are mild, and this type of compound can be obtained in good yield, and the product is stable. the
具体实施方式 Detailed ways
结合以下具体实施例，对本发明作进一步的详细说明。实施本发明的过程、条件、试剂、实验方法等，除以下专门提及的内容之外，均为本领域的普遍知识和公知常识，本发明没有特别限制内容。 In conjunction with the following specific examples, the present invention is further described in detail. The process, conditions, reagents, experimental methods, etc. for implementing the present invention are general knowledge and common knowledge in the art except for the content specifically mentioned below, and the present invention has no special limitation content. the
本发明提供了一种2，3，4，6-四取代苯酚类衍生物的合成方法，在室温和氮气保护下，把烯炔醚类化合物和1，3-二羰基类化合物在催化剂铁盐、无机碱存在下，于适当溶剂中，升温至35℃，反应1-16小时，经分离提纯后，得到多取代苯酚类衍生物，烯炔醚：1，3-二羰基化合物：无机碱：铁盐的摩尔比为1.0：2.0：2.0：0.1，收率48-84％。本方法中，适用的铁盐包括Fe(ClO4)39H2O、Fe(SO4)3、FeCl3等，适用的无机碱为Cs2CO3，适用的溶剂为N，N-二甲基甲酰胺(DMF)。 The present invention provides a kind of synthetic method of 2,3,4,6-tetrasubstituted phenol derivatives, at room temperature and under the protection of nitrogen, enyne ether compounds and 1,3-dicarbonyl compounds in catalyst iron salt 1. In the presence of an inorganic base, in a suitable solvent, heat up to 35°C, react for 1-16 hours, and after separation and purification, obtain multi-substituted phenol derivatives, enyne ether: 1,3-dicarbonyl compound: inorganic base: The molar ratio of the iron salt is 1.0:2.0:2.0:0.1, and the yield is 48-84%. In this method, the applicable iron salts include Fe(ClO 4 ) 3 9H 2 O, Fe(SO 4 ) 3 , FeCl 3 , etc., the applicable inorganic base is Cs 2 CO 3 , and the applicable solvent is N,N-dimethyl methyl formamide (DMF).
以下是本发明制备方法的反应简式： Below is the reaction brief formula of preparation method of the present invention:
其中，R1＝C1-20的烷基、乙氧基；R2为C1-20的烷基；R3为吸电子基(卤素)、供电子基(烷基、烷氧基)。 Wherein, R 1 =C 1-20 alkyl, ethoxy; R 2 is C 1-20 alkyl; R 3 is electron withdrawing group (halogen), electron donating group (alkyl, alkoxy).
以下通过实施例进一步说明本发明的技术方案。所有的实施例均按照上述的合成方法进行操作，所列举的技术参数仅仅为实施参考用。在本发明提及的条件下进行制备，均能制备得到目标化合物，收率达到50-84％。 The technical scheme of the present invention is further illustrated below by way of examples. All the examples are operated according to the above-mentioned synthesis method, and the listed technical parameters are only for reference. Under the conditions mentioned in the present invention, the target compound can be prepared, and the yield can reach 50-84%. the
实施例1：2-苯基-3-甲基-4-乙酰基-6-甲酸乙酯基苯酚
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl2-(phenoxymethylene)-4-phenylbut-3-ynoate、乙酰丙酮、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚炔0.3mmol、乙酰丙酮0.6mmol、无机碱0.6mmol、溶剂3ml、铁盐0.03mmol，在35℃反应1小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0：0.1，得目标产物，黄色固体，收率84％。 Enyne ethers, 1,3-dicarbonyl compounds, inorganic bases, iron salts, and solvents were selected from (E)-Ethyl2-(phenoxymethylene)-4-phenylbut-3-ynoate, acetylacetone, Cs 2 CO 3 , Fe(ClO 4 ) 3 9H 2 O, N, N-dimethylformamide, the amount of raw materials used is 0.3mmol of enyne ether alkyne, 0.6mmol of acetylacetone, 0.6mmol of inorganic base, 3ml of solvent, and 0.03mmol of iron salt, and react at 35°C For 1 hour, the ratio of enyne ether: acetylacetone: inorganic base: iron salt was 1.0:2.0:2.0:0.1, and the target product was obtained as a yellow solid with a yield of 84%.
1H NMR(400MHZ，CDCl3，Me4Si)δ1.36(t，3H)，2.19(s，3H)，2.54(s，3H)，4.37(q，2H)，7.12(d，J＝7.2Hz，2H)，7.30-7.40(m，3H)，8.19(s，1H)，11.34(s，1H)；13C NMR(100.6MHZ，CDCl3，Me4Si)13.88，19.18，29.37，61.77，109.56，127.76，128.67，130.02，130.60，131.05，132.86，136.16，145.68，161.76，170.20，200.75.高分辨质谱(ESI)C18H19O4(M+H)，理论值：299.1283，实测值：299.1266。 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ1.36(t, 3H), 2.19(s, 3H), 2.54(s, 3H), 4.37(q, 2H), 7.12(d, J= 7.2Hz, 2H), 7.30-7.40(m, 3H), 8.19(s, 1H), 11.34(s, 1H); 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) 13.88, 19.18, 29.37, 61.77, 109.56, 127.76, 128.67, 130.02, 130.60, 131.05, 132.86, 136.16, 145.68, 161.76, 170.20, 200.75. High resolution mass spectrum (ESI) C 18 H 19 O 4 (M+H), theoretical value: 299.1283 Value: 299.1266.
实施例2：2-苯基-3-乙基-4-丙酰基-6-甲酸乙酯基苯酚
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl2-(phenoxymethylene)-4-phenylbut-3-ynoate、3，5-庚烷二酮、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚0.3mmol、乙酰丙酮0.6mmol、无机碱0.6mmol、溶剂3ml、铁盐0.03mmol，在35℃反应5小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0：0.1，得目标产物，淡黄色液体，收率72％。 Enyne ethers, 1,3-dicarbonyl compounds, inorganic bases, iron salts, and solvents were selected from (E)-Ethyl2-(phenoxymethylene)-4-phenylbut-3-ynoate, 3,5-heptanedione, and Cs 2 CO 3 , Fe(ClO 4 ) 3 9H 2 O, N,N-dimethylformamide, the amount of raw materials used is 0.3mmol of enyne ether, 0.6mmol of acetylacetone, 0.6mmol of inorganic base, 3ml of solvent, and 0.03mmol of iron salt , reacted at 35°C for 5 hours, the ratio of enyne ether: acetylacetone: inorganic base: iron salt was 1.0: 2.0: 2.0: 0.1, and the target product was obtained as a light yellow liquid with a yield of 72%.
1H NMR(400MHZ，CDCl3，Me4Si)δ0.95(t，3H)，1.23(t，3H)，1.44(t，3H)，2.68(q，2H)，2.97(q，2H)，4.44(q，2H)，7.22(d，J＝7.2Hz，2H)，7.38-7.48(m，3H)，8.19(s，1H)，11.34(s，1H).13C NMR(100.6MHZ，CDCl3，Me4Si)δ8.21，13.90，15.17，23.75，34.82，61.70，109.54，127.70，128.51，130.03，130.20，130.48，132.42，136.00，151.26，161.59，170.17，204.33高分辨质谱(ESI)C20H23O4(M+H)，理论值：327.1596，实测值：327.1596。 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ0.95(t, 3H), 1.23(t, 3H), 1.44(t, 3H), 2.68(q, 2H), 2.97(q, 2H) , 4.44(q, 2H), 7.22(d, J=7.2Hz, 2H), 7.38-7.48(m, 3H), 8.19(s, 1H), 11.34(s, 1H). 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) δ8.21, 13.90, 15.17, 23.75, 34.82, 61.70, 109.54, 127.70, 128.51, 130.03, 130.20, 130.48, 132.42, 136.00, 151.26, 161.59, 1704.13 ) C 20 H 23 O 4 (M+H), calc: 327.1596, found: 327.1596.
实施例3：2-(4-甲基)苯基-3-甲基-4-乙酰基-6-甲酸乙酯基苯酚
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl2-(phenoxymethylene)-4-p-tolylbut-3-ynoate、乙酰丙酮、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚0.3mmol、乙酰丙酮0.6mmol、无机碱0.6mmol、溶剂3ml、铁盐0.03mmol，在35℃反应3小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0： 0.1，得目标产物，淡黄色固体，收率68％。 Enyne ethers, 1,3-dicarbonyl compounds, inorganic bases, iron salts, and solvents were selected from (E)-Ethyl2-(phenoxymethylene)-4-p-tolylbut-3-ynoate, acetylacetone, Cs 2 CO 3 , Fe (ClO 4 ) 3 9H 2 O, N,N-dimethylformamide, the amount of raw materials used is 0.3mmol of enyne ether, 0.6mmol of acetylacetone, 0.6mmol of inorganic base, 3ml of solvent, and 0.03mmol of iron salt, at 35°C After 3 hours of reaction, the ratio of enyne ether: acetylacetone: inorganic base: iron salt was 1.0: 2.0: 2.0: 0.1, and the target product was obtained as a light yellow solid with a yield of 68%.
1H NMR(400MHZ，CDCl3，Me4Si)δ1.36(t，3H)，2.20(s，3H)，2.32(s，3H)，2.53(s，3H)，4.37(q，2H)，7.00(d，J＝7.6Hz，2H)，7.19d，J＝7.6Hz，2H)，，8.18(s，1H)，11.34(s，1H).13C NMR(100.6MHZ，CDCl3，Me4Si)δ13.88，19.19，20.97，29.35，61.73，109.46，129.44，129.83，130.55，130.92，132.84，133.01，137.45，145.77，161.85，170.22，200.77高分辨质谱(ESI)C19H21O4(M+H)，理论值：313.1440，实测值：313.1440。 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ1.36(t, 3H), 2.20(s, 3H), 2.32(s, 3H), 2.53(s, 3H), 4.37(q, 2H) , 7.00(d, J=7.6Hz, 2H), 7.19d, J=7.6Hz, 2H), , 8.18(s, 1H), 11.34(s, 1H). 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) δ13.88, 19.19, 20.97, 29.35, 61.73, 109.46, 129.44, 129.83, 130.55, 130.92, 132.84, 133.01, 137.45, 145.77, 161.85, 170.22, 200.77 2C high resolution mass spectrum ( O9 HI 4 (M+H), theoretical value: 313.1440, found value: 313.1440.
实施例4：2-(4-甲氧基)苯基-3-甲基-4-乙酰基-6-甲酸乙酯基苯酚
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl4-(4-methoxyphenyl)-2-(phenoxymethylene)but-3-ynoate、乙酰丙酮、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚0.3mmol、乙酰丙酮0.6mmol、无机碱0.6mmol、溶剂3ml、铁盐0.03mmol，在35℃反应2小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0：0.1，得目标产物，淡黄色固体，收率61％。 Enyne ethers, 1,3-dicarbonyl compounds, inorganic bases, iron salts, and solvents were selected from (E)-Ethyl4-(4-methoxyphenyl)-2-(phenoxymethylene)but-3-ynoate, acetylacetone, and Cs 2 CO 3. Fe(ClO 4 ) 3 9H 2 O, N,N-dimethylformamide, the amount of raw materials is 0.3mmol of enyne ether, 0.6mmol of acetylacetone, 0.6mmol of inorganic base, 3ml of solvent, and 0.03mmol of iron salt, Reaction at 35°C for 2 hours, the ratio of enyne ether: acetylacetone: inorganic base: iron salt was 1.0:2.0:2.0:0.1, and the target product was obtained as a light yellow solid with a yield of 61%.
1H NMR(400MHZ，CDCl3，Me4Si)δ1.36(t，3H)，2.20(s，3H)，2.53(s，3H)，3.76(s，2H)，4.37(q，2H)，6.91(d，J＝8.0Hz，2H)，7.04(d，J＝8.4Hz，2H)，8.17(s，1H)，11.35(s，1H). 13C NMR(100.6MHZ，CDCl3，Me4Si)δ13.86，19.20，29.33，55.02，61.73，109.47，114.07，128.08，130.61，130.85，131.14，132.50，145.95，159.27，162.00，170.24，200.77.高分辨质谱(ESI)C19H21O5(M+H)，理论值：329.1389，实测值：329.1387。 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ1.36(t, 3H), 2.20(s, 3H), 2.53(s, 3H), 3.76(s, 2H), 4.37(q, 2H) , 6.91(d, J=8.0Hz, 2H), 7.04(d, J=8.4Hz, 2H), 8.17(s, 1H), 11.35(s, 1H). 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) δ13.86, 19.20, 29.33, 55.02, 61.73, 109.47, 114.07, 128.08, 130.61, 130.85, 131.14, 132.50, 145.95 , 159.27, 162.00, 170.24, 200.77 . O 5 (M+H), Cal.: 329.1389, Found: 329.1387.
实施例5：2-(4-氯)苯基-3-甲基-4-乙酰基-6-甲酸乙酯基苯酚的合成 Example 5: 2-(4-chloro)phenyl-3-methyl-4-acetyl-6-carboxyethyl phenol Synthesis
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl4-(4-chlorophenyl)-2-(phenoxymethylene)but-3-ynoate、乙酰丙酮、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚0.3mmol、乙酰丙酮0.6mmol、无机碱0.6mmol、溶剂3ml、铁盐0.03mmol，在35℃反应3小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0：0.1，得目标产物，淡黄色固体，收率50％。 Enyne ethers, 1,3-dicarbonyl compounds, inorganic bases, iron salts, and solvents were selected from (E)-Ethyl4-(4-chlorophenyl)-2-(phenoxymethylene)but-3-ynoate, acetylacetone, and Cs 2 CO 3. Fe(ClO 4 ) 3 9H 2 O, N,N-dimethylformamide, the amount of raw materials is 0.3mmol of enyne ether, 0.6mmol of acetylacetone, 0.6mmol of inorganic base, 3ml of solvent, and 0.03mmol of iron salt, Reaction at 35°C for 3 hours, the ratio of enyne ether: acetylacetone: inorganic base: iron salt was 1.0:2.0:2.0:0.1, and the target product was obtained as a light yellow solid with a yield of 50%.
1H NMR(400MHZ，CDCl3，Me4Si)δ1.37(t，3H)，2.19(s，3H)，2.54(s，3H)，4.38(q，2H)，7.05-7.07(m，2H)，7.35-7.37(m，2H)，8.19(s，1H)，11.37(s，1H)13C NMR(100.6MHZ，CDCl3，Me4Si)δ13.90，19.18，29.36，61.89，109.69，128.98，130.67，131.28，131.56，131.61，133.86，134.55，145.64，161.66，170.15，200.63.高分辨质谱(ESI)C18H18ClO4(M+H)，理论值：333.0894，实测值：333.0891。 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ1.37(t, 3H), 2.19(s, 3H), 2.54(s, 3H), 4.38(q, 2H), 7.05-7.07(m, 2H), 7.35-7.37(m, 2H), 8.19(s, 1H), 11.37(s, 1H) 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) δ13.90, 19.18, 29.36, 61.89, 109.69, 128.98, 130.67, 131.28, 131.56, 131.61, 133.86, 134.55, 145.64, 161.66, 170.15, 200.63. High resolution mass spectrum (ESI) C 18 H 18 ClO 4 (M+H), theoretical value: 333.0894, measured value 333.0891.
实施例6：2-苯基-3-甲基-4，6-二甲酸乙酯基苯酚
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl4-(4-methoxyphenyl)-2-(phenoxymethylene)but-3-ynoate、乙酰乙酸乙酯、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚0.3mmol、乙酰丙酮0.6mmol、无机碱0.6 mmol、溶剂3ml、铁盐0.03mmol，在35℃反应16小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0：0.1，得目标产物，淡黄色固体，收率51％。 Enyne ether, 1,3-dicarbonyl compound, inorganic base, iron salt, and solvent are respectively selected from (E)-Ethyl4-(4-methoxyphenyl)-2-(phenoxymethylene)but-3-ynoate, ethyl acetoacetate, Cs 2 CO 3 , Fe(ClO 4 ) 3 9H 2 O, N,N-dimethylformamide, the amount of raw materials used is 0.3mmol of enyne ether, 0.6mmol of acetylacetone, 0.6mmol of inorganic base, 3ml of solvent, and 0.03mmol of iron salt mmol, reacted at 35°C for 16 hours, the ratio of enyne ether: acetylacetone: inorganic base: iron salt was 1.0:2.0:2.0:0.1, and the target product was obtained as a light yellow solid with a yield of 51%.
1H NMR(400MHZ，CDCl3，Me4Si)δ1.35(m，6H)，2.26(s，3H)，4.29(q，2H)，2.4.37(q，2H)，7.13(d，J＝6.8Hz，2H)，7.31-7.40(m，3H)，8.38(s，1H)，11.33(s，1H).13C NMR(100.6MHZ，CDCl3，Me4Si)δ13.88，14.03，19.13，60.77，61.70，110.06，122.51，127.73，128.67，130.11，132.27，132.42，136.35，146.61，161.85，167.62，170.39.高分辨质谱(ESI)C19H21O5(M+H)，理论值：329.1389，实测值：329.1389。 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ1.35(m, 6H), 2.26(s, 3H), 4.29(q, 2H), 2.4.37(q, 2H), 7.13(d, J=6.8Hz, 2H), 7.31-7.40(m, 3H), 8.38(s, 1H), 11.33(s, 1H). 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) δ13.88, 14.03, 19.13, 60.77, 61.70, 110.06, 122.51, 127.73, 128.67, 130.11, 132.27, 132.42, 136.35, 146.61, 161.85, 167.62 , 170.39. High resolution mass spectrum (ESI) C 19 HM+H 21 O) Theoretical value: 329.1389, measured value: 329.1389.
实施例7：2-(1-萘基)-3-甲基-4-乙酰基-6-甲酸乙酯基苯酚的合成 Example 7: 2-(1-naphthyl)-3-methyl-4-acetyl-6-carboxyethyl phenol Synthesis
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl4-(4-naphthalen-1-yl)-2-(phenoxymethylene)but-3-ynoate、乙酰丙酮、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚0.3mmol、乙酰丙酮0.6mmol、无机碱0.6mmol、溶剂3ml、铁盐0.03mmol，在35℃反应2小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0：0.1，得目标产物，黄色固体，收率77％。 Enyne ether, 1,3-dicarbonyl compound, inorganic base, iron salt, and solvent are respectively selected from (E)-Ethyl4-(4-naphthalen-1-yl)-2-(phenoxymethylene)but-3-ynoate, acetylacetone . _ _ _ _ Salt 0.03mmol, reacted at 35°C for 2 hours, enyne ether: acetylacetone: inorganic base: iron salt was 1.0:2.0:2.0:0.1, and the target product was obtained as a yellow solid with a yield of 77%.
1H NMR(400MHZ，CDCl3，Me4Si)δ1.34(t，3H)，2.08(s，3H)，2.56(s，3H)，4.35(q，2H)，7.21(d，J＝6.8Hz，1H)，7.27-7.28(m，2H)，7.36-7.38(m，1H)，7.47(t，1H).13C NMR(100.6MHZ，CDCl3，Me4Si)δ13.88，18.85，29.35，61.80，109.68，125.14，125.75，126.12，126.47，127.62，128.40，128.70，130.58，130.80，131.52，132.06，133.92，133.96，146.89，162.22，170.13，200.64.高分辨质谱(ESI)C22H21O4(M+H)，理论值：349.1440，实测值：349.1433. 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ1.34(t, 3H), 2.08(s, 3H), 2.56(s, 3H), 4.35(q, 2H), 7.21(d, J= 6.8Hz, 1H), 7.27-7.28(m, 2H), 7.36-7.38(m, 1H), 7.47(t, 1H). 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) δ13.88, 18.85，29.35，61.80，109.68，125.14，125.75，126.12，126.47，127.62，128.40，128.70，130.58，130.80，131.52，132.06，133.92，133.96，146.89，162.22，170.13，200.64.高分辨质谱(ESI)C 22 H 21 O 4 (M+H), theoretical value: 349.1440, found value: 349.1433.
实施例8：2-(3，4，5-三甲氧基)苯基-3-甲基-4-乙酰基-6-甲酸乙酯基苯酚
烯炔醚、1，3-二羰基化合物、无机碱、铁盐、溶剂分别选用(E)-Ethyl2-(phenoxymethylene)-4-(3，4，5-trimethoxyphenyl)but-3-ynoate、乙酰丙酮、Cs2CO3、Fe(ClO4)39H2O、N，N-二甲基甲酰胺，原料的用量为烯炔醚0.3mmol、乙酰丙酮0.6mmol、无机碱0.6mmol、溶剂3ml、铁盐0.03mmol，在35℃反应5小时，烯炔醚：乙酰丙酮：无机碱：铁盐为1.0：2.0：2.0：0.1，得目标产物，白色固体，收率48％。 Enyne ether, 1,3-dicarbonyl compound, inorganic base, iron salt, and solvent are respectively selected from (E)-Ethyl2-(phenoxymethylene)-4-(3,4,5-trimethoxyphenyl)but-3-ynoate, acetylacetone . _ _ _ _ Salt 0.03mmol, reacted at 35°C for 5 hours, enyne ether: acetylacetone: inorganic base: iron salt was 1.0:2.0:2.0:0.1, and the target product was obtained as a white solid with a yield of 48%.
1H NMR(400MHZ，CDCl3，Me4Si)δ1.46(t，3H)，2.31(s，3H)，2.63(s，3H)，3.85(s，6H)，3.92(s，3H)，4.48(q，2H)，6.42(s，2H)，8.27(s，1H)，11.50(s，1H).13C NMR(100.6MHZ，CDCl3，Me4Si)δ13.86，19.14，29.33，55.88，60.70，61.82，106.82，109.53，130.67，130.89，131.57，132.79，137.45，145.84，153.64，161.62，170.18，200.73.高分辨质谱(ESI)C21H25O7(M+H)，理论值：389.1600，实测值：389.1602. 1 H NMR (400MH Z , CDCl 3 , Me 4 Si) δ1.46(t, 3H), 2.31(s, 3H), 2.63(s, 3H), 3.85(s, 6H), 3.92(s, 3H) , 4.48(q, 2H), 6.42(s, 2H), 8.27(s, 1H), 11.50(s, 1H). 13 C NMR (100.6MH Z , CDCl 3 , Me 4 Si) δ13.86, 19.14, 29.33, 55.88, 60.70, 61.82, 106.82, 109.53, 130.67, 130.89, 131.57, 132.79, 137.45, 145.84, 153.64, 161.62, 170.18 , 200.73. High resolution mass spectrum (ESI) C 27 HM+H 25 O ) Theoretical value: 389.1600, measured value: 389.1602.
本发明的保护内容不局限于以上实施例。在不背离发明构思的精神和范围下，本领域技术人员能够想到的变化和优点都被包括在本发明中，并且以所附的权利要求书为保护范围。 The protection content of the present invention is not limited to the above embodiments. Without departing from the spirit and scope of the inventive concept, changes and advantages conceivable by those skilled in the art are all included in the present invention, and the appended claims are the protection scope. the
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| MOHANAD SHKOOR，ET AL.: "Diversity-oriented synthesis of 1-hydroxy-2,4-benzodioates by regioselective [3+3] cyclocondensations of 1,3-bis(silyloxy)-1,3-butadienes with 3-alkoxyand 3-silyloxy-2-alkoxycarbonyl-2-en-1-ones", 《ORG. BIOMOL. CHEM.》, vol. 7, 31 March 2009 (2009-03-31), pages 2182 - 2186 * |
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