阅读说明：本技术 一种二茂铁基查尔酮的合成及其应用 (Synthesis and application of ferrocenyl chalcone ) 是由 尹大伟 王龙瑞 刘玉婷 刘�英 李金泽 于 2021-09-28 设计创作，主要内容包括：本发明公开了一种二茂铁基查尔酮的合成及其应用,属于化学合成技术领域。向干燥的研钵中依次加入碘、乙酰二茂铁和芳醛混合。TLC监测直至反应完全,反应完全后采用硫代硫酸钠溶液冲洗,抽滤,水洗,干燥得粗品。本发明采用无溶剂法合成二茂铁查尔酮,操作简单,产率高,反应条件温和,反应时间短,且绿色环保,成本低廉等优点。其中,由于不饱和键的存在,本发明还对该类化合物在不同的金属离子下进行选择性检测,对金属离子有很好的识别作用,实验表明该类化合物的合成和发展具有重要的意义。同时二茂铁基查尔酮含有α-β不饱和双键和羰基不饱和碱,对阳离子的检测提供了一种可能性。(The invention discloses synthesis and application of ferrocenyl chalcone, and belongs to the technical field of chemical synthesis. Adding iodine, acetyl ferrocene and aromatic aldehyde into a dry mortar in sequence for mixing. And monitoring by TLC until the reaction is complete, washing by using a sodium thiosulfate solution after the reaction is complete, carrying out suction filtration, washing by water, and drying to obtain a crude product. The invention adopts a solvent-free method to synthesize the ferrocene chalcone, and has the advantages of simple operation, high yield, mild reaction conditions, short reaction time, environmental protection, low cost and the like. Due to the existence of unsaturated bonds, the invention also carries out selective detection on the compounds under different metal ions, has good identification effect on the metal ions, and experiments show that the synthesis and development of the compounds have important significance. Meanwhile, the ferrocenyl chalcone contains an alpha-beta unsaturated double bond and carbonyl unsaturated alkali, and provides a possibility for detecting cations.)

1. A preparation method of ferrocenyl chalcone is characterized in that acetyl ferrocene and aromatic aldehyde are subjected to claisen-Schmitt reaction to obtain the ferrocenyl chalcone.

2. The method for producing ferrocenyl chalcone according to claim 1, wherein a catalyst is further added during the claisen-schmitt reaction.

3. The method for preparing ferrocenyl chalcone according to claim 1, wherein the catalyst is iodine.

4. The method for preparing ferrocenyl chalcone according to claim 1, wherein the molar ratio of the acetyl ferrocene to the aromatic aldehyde is 1: (1-1.4).

5. The method for preparing ferrocenyl chalcone according to claim 2, wherein the molar ratio of the acetyl ferrocene to the catalyst is 1: (0.1-0.2).

6. The method for preparing ferrocenyl chalcone according to claim 2, wherein the preparation process specifically comprises:

step 1) grinding and mixing acetyl ferrocene and aromatic aldehyde, performing claisen-Schmitt reaction, and simultaneously performing TLC monitoring;

and 2) obtaining a mixed solution after the Clisen-Schmitt reaction is finished, and washing and drying the mixed solution to obtain the ferrocenyl chalcone.

7. The method for preparing ferrocenyl chalcone according to claim 1, wherein the claisen-schmitt reaction conditions are as follows: the temperature is 25 deg.C, and the time is 5-10 min.

8. A method for preparing ferrocenyl chalcone according to claim 6, wherein in the step 2), the washing is performed by mixing with a sodium thiosulfate solution;

the mass fraction of the sodium thiosulfate solution is 5%.

9. Use of ferrocenyl chalcone prepared by the method according to any one of claims 1 to 8 in metal ion detection, wherein the metal ion is Al³⁺，Sn²⁺，Ba²⁺，Cu²⁺，Mn²⁺，Fe²⁺，Li⁺，Ca²⁺，K⁺，Fe³⁺And Co²⁺。

Technical Field

The invention belongs to the technical field of chemical synthesis, and relates to synthesis and application of ferrocenyl chalcone.

Background

Chalcone is one kind of flavonoid, exists in safflower, licorice and other plant species, and its mother body has bioactivity and pharmacological activity and may be used in resisting bacteria, diminishing inflammation, resisting tumor, resisting virus, etc; the ferrocene also has good biological activity, and the synthesized ferrocenyl chalcone has better activity by the principle of activity superposition, is used in the field of medicine, and plays a good role in the aspects of treating cancers, tumors and the like. Meanwhile, the ferrocenyl chalcone is an important intermediate for organic synthesis, and can be used for preparing the ferrocene derivative containing the heterocycle.

Fe³⁺Ions are crucial to life processes, and many enzymes in organisms use iron as a catalyst to complete oxygen metabolism and electron transfer, and DNA and RNA synthesis. Fe in human body³⁺Ion deficiency or excess can cause serious diseases, and chlorosis caused by iron deficiency is a widely existing agricultural production problem, which can lead to reduced yield of crops. Therefore, there is an urgent need to develop a method capable of detecting Fe in environment and biological samples³⁺Research on chemical sensors of ions. To date, many host molecules have been synthesized, including derivatives such as schiff bases, ketenes, carbazoles, rhodamines, and the like. These host molecules are other than for Fe³⁺Besides the recognition function, most ions also respond to other ions, so that the selectivity is affected.

The ferrocenyl chalcone contains alpha-beta unsaturated double bond and can carry out addition reaction on the double bond. Ferrocenyl chalcones are typically prepared from acetylferrocene and an aromatic aldehyde by the claisen-schmitt reaction. The traditional synthetic method is a liquid phase method, namely, the catalyst is NaOH in an ethanol solution, and the NaOH is heated and refluxed to obtain the catalyst, but the reaction time is long, the using amount of the solvent is large, and the post-treatment is complicated. Therefore, the method for synthesizing the chalcone containing ferrocenyl, which has the advantages of short reaction time, high yield and simple and convenient operation, has certain significance.

Disclosure of Invention

The invention aims to overcome the defects of long reaction time, large solvent consumption and complicated post-treatment of the ferrocenyl chalcone synthesis method in the prior art, and provides synthesis and application of the ferrocenyl chalcone.

In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:

a preparation method of ferrocenyl chalcone comprises the step of performing claisen-Schmitt reaction on acetyl ferrocene and aromatic aldehyde to obtain the ferrocenyl chalcone.

Preferably, a catalyst is also added during the claisen-schmitt reaction.

Preferably, the catalyst is iodine.

Preferably, the molar ratio of acetylferrocene to aromatic aldehyde is 1: (1-1.4).

Preferably, the molar ratio of acetylferrocene to catalyst is 1: (0.1-0.2).

Preferably, the preparation process specifically comprises the following steps:

step 1) grinding and mixing acetyl ferrocene and aromatic aldehyde, performing claisen-Schmitt reaction, and simultaneously performing TLC monitoring;

and 2) obtaining a mixed solution after the Clisen-Schmitt reaction is finished, and washing and drying the mixed solution to obtain the ferrocenyl chalcone.

Preferably, the conditions of the claisen-schmitt reaction are: the temperature is 25 deg.C, and the time is 5-10 min.

Preferably, the washing is carried out by mixing with a sodium thiosulfate solution;

the mass fraction of the sodium thiosulfate solution is 5%.

Application of ferrocenyl chalcone prepared by the method in metal ion detection, wherein metal ions are Al³⁺，Sn²⁺，Ba²⁺，Cu²⁺，Mn²⁺，Fe²⁺，Li⁺，Ca²⁺，K⁺，Fe³⁺And Co²⁺。

Compared with the prior art, the invention has the following beneficial effects:

the invention also discloses a preparation method of the ferrocenyl chalcone, which comprises the step of sequentially adding iodine, acetyl ferrocene and aromatic aldehyde into a dry mortar for mixing. And monitoring by TLC until the reaction is complete, washing by using a sodium thiosulfate solution after the reaction is complete, carrying out suction filtration, washing by water, and drying to obtain a crude product. The invention adopts a solvent-free method to synthesize the ferrocene chalcone, and has the advantages of simple operation, high yield, mild reaction conditions, short reaction time, environmental protection, low cost and the like. Due to the existence of unsaturated bonds, the invention also carries out selective detection on the compounds under different metal ions, has good identification effect on the metal ions, and experiments show that the synthesis and development of the compounds have important significance. Meanwhile, the ferrocenyl chalcone contains an alpha-beta unsaturated double bond and carbonyl unsaturated alkali, and provides a possibility for detecting cations.

Drawings

FIG. 1 is a FT-IR spectrum of 1-phenyl-3-ferrocenyl ketene;

FIG. 2 is 1-phenyl-3-ferrocenylenone¹H NMR spectrum;

FIG. 3 is 1-phenyl-3-ferrocenylenone¹³C NMR spectrum;

FIG. 4 is a FT-IR spectrum of 1- (4-fluoro) phenyl-3-ferrocenylenone;

FIG. 5 is 1- (4-fluoro) phenyl-3-ferrocenylenone¹H NMR spectrum;

FIG. 6 is 1- (4-fluoro) phenyl-3-ferrocenylenone¹³C NMR spectrum;

FIG. 7 is a graph of the UV-VIS absorption spectrum of 1-phenyl-3-ferrocenylenone on different metal ions;

FIG. 8 is a graph of the UV-VIS absorption spectrum of 1- (2-hydroxy) phenyl-3-ferrocenylenone on different metal ions;

FIG. 9 is a synthetic scheme of the preparation method of the present invention.

Detailed Description

The invention is described in further detail below with reference to the accompanying drawings:

example 1

Preparation of 1-phenyl-3-ferrocenyl ketene

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; adding 0.1378g (1.3mmol) of benzaldehyde into the reaction system, grinding at room temperature for 5-10min, and monitoring by TLC until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The infrared characterization of the product is shown in fig. 1, from which it can be seen that: IR (KBr) v 3093cm^-1(-CH＝)，1674cm^-1(C＝O)，1624cm^-1(C＝C)，1493cm^-1，1450cm^-1(Ar，Fc)，742cm^-1，702cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:4.25(s，5H，Fc-H)，4.63(s，2H，Fc-H)，4.95(s，2H，Fc-H)，7.14-7.18(d，1H，＝CH)，7.29-7.68(m，5H，Ph-H)，7.81-7.85(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.47，140.38，134.70，129.63，128.46，127.79，122.46，80.12，72.31，69.63，69.25。

Example 2

Preparation of 1- (4-methyl) phenyl-3-ferrocenylenone

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1560g (1.3mmol) of 4-methylbenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The infrared characterization of the product is shown in fig. 2, from which it can be seen that: IR (KBr) v 3098cm^-1(-CH＝)，2980，1370cm^-1(-CH₃)，1647cm^-1(C＝O)，1590cm^-1(C＝C)，1503cm^-1，1434cm^-1(Ar，Fc)，809cm^-1(Ar-H)。

¹H NMR(400MHz，DMSO-d₆)，δ:2.43(s，3H，-CH₃)，4.23(s，5H，Fc-H)，4.62(s，2H，Fc-H)，4.93(s，2H，Fc-H)，7.12～7.16(d，1H，＝CH)，7.27～7.30(d，2H，Ph-H)，7.58～7.60(d，2H，Ph-H)，7.80～7.84(d，1H，＝CH)。

¹³C NMR(100MHz，DMSO-d₆)，δ:192.58，140.43，140.09，131.85，129.42，127.79，122.46，80.12，72.31，69.63，69.25，21.06。

Example 3

Preparation of 1- (4-hydroxy) phenyl-3-ferrocenylenone

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1586g (1.3mmol) of 4-hydroxybenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The infrared characterization of the product is shown in fig. 3, from which it can be seen that: IR (KBr) v 3465cm^-1(-OH)，3075cm^-1(-CH＝)，1653cm^-1(C＝O)，1585cm^-1(C＝C)，1503cm^-1，1434cm^-1(Ar，Fc)，812cm^-1(Ar-H)。

¹H NMR(400MHz，DMSO-d₆)，δ:4.23(s，5H，Fc-H)，4.62(s，2H，Fc-H)，4.93(s，2H，Fc-H)，7.12～7.16(d，1H，＝CH)，7.27～7.30(d，2H，Ph-H)，7.58～7.60(d，2H，Ph-H)，7.80～7.84(d，1H，＝CH)，9.59(s，1H，-OH)。

¹³C NMR(100MHz，DMSO-d₆)，δ:193.58，136.42，134.02，129.12，123.79，121.46，80.12，72.31，69.63，69.25，21.06。

Example 4

Preparation of 1- (4-nitro) phenyl-3-ferrocenylenone

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1963g (1.3mmol) of 4-nitrobenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The infrared characterization of the product is shown in fig. 4, from which it can be seen that: IR (KBr) v 3096cm^-1(-CH＝)，1658cm^-1(C＝O)，1583cm^-1(C＝C)，1507cm^-1，1458cm^-1(Ar，Fc)，1365cm^-1(-N＝O)，815cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:4.24(s，5H，Fc-H)，4.54(s，2H，Fc-H)，4.80(s，2H，Fc-H)，7.26-7.29(d，1H，＝CH)，7.57-7.59(d，2H，Fc-H)，7.80-7.82(d，2H，Fc-H)，8.12-8.13(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.65，137.44，134.00，129.55，124.99，123.81，121.48，80.01，72.81，69.75，69.40。

Example 5

Preparation of 1- (4-fluoro) phenyl-3-ferrocenylenone

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; adding 0.1612g (1.3mmol) of 4-fluorobenzaldehyde into the reaction system, grinding at room temperature for 5-10min, and monitoring by TLC until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The infrared characterization of the product is shown in figure 5,from the results, it can be seen that: IR (KBr) v 3096cm^-1(-CH＝)，1648cm^-1(C＝O)，1583cm^-1(C＝C)，1507cm^-1，1458cm^-1(Ar，Fc)，819cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:4.25(s，5H，Fc-H)，4.53(s，2H，Fc-H)，4.80(s，2H，Fc-H)，7.06-7.15(d，1H，＝CH)，7.29-7.30(d，2H，Ph-H)，7.67-7.69(d，2H，Ph-H)，7.77-7.80(1，2H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.30，139.12，130.90，129.67，122.15，115.71，115.49，80.03，72.36，69.63，69.39。

Example 6

Preparation of 1- (4-chloro) phenyl-3-ferrocenylenone

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1820g (1.3mmol) of 4-chlorobenzaldehyde is added into the reaction system, the mixture is ground for 5-10min at room temperature, and TLC is used for monitoring until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The infrared characterization of the product is shown in fig. 6, from which it can be seen that: IR (KBr) v 3096cm^-1(-CH＝)，1648cm^-1(C＝O)，1583cm^-1(C＝C)，1507cm^-1，1458cm^-1(Ar，Fc)，817cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:4.24(s，5H，Fc-H)，4.63(s，2H，Fc-H)，4.83(s，2H，Fc-H)，7.09-7.13(d，1H，＝CH)，7.41-7.43(d，2H，Ph-H)，7.60-7.62(d，2H，Ph-H)，7.74-7.78(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.23，138.93，136.78，133.19，128.94，128.72，122.87，79.97，72.44，69.66，69.26。

Example 7

Preparation of 1- (4-methoxy) phenyl-3-ferrocenyl ketene

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1768g (1.3mmol) of 4-methoxybenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The structural characterization data for the product is: IR (KBr) v 3086cm^-1(-CH＝)，2896cm^-1，1349cm^-1(-CH₃)，1648cm^-1(C＝O)，1583cm^-1(C＝C)，1507cm^-1，1459cm^-1(Ar，Fc)，819cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:3.89(s，3H，-OCH₃)，4.24(s，5H，Fc-H)，4.60(s，2H，Fc-H)，4.94(s，2H，Fc-H)，6.98-7.03(d，1H，＝CH)，7.64-7.65(d，2H，Ph-H)，7.78-7.81(d，2H，Ph-H)，7.87-7.90(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.53，140.17，131.50，129.42，127.37，120.23，113.90，80.15，72.11，69.39，69.19，54.95。

Example 8

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1924g (1.3mmol) of 4-isopropylbenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The structural characterization data for the product is: IR (KBr) v 3096cm^-1(-CH＝)，2958cm^-1，1371cm^-1(-CH₃)，1649cm^-1(C＝O)，1585cm^-1(C＝C)，1513cm^-1，1442cm^-1(Ar，Fc)，812cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:1.30(s，6H，-CH₃)，2.97(m，1H，-CH)，4.24(s，5H，Fc-H)，4.60(s，2H，Fc-H)，4.94(s，2H，Fc-H)，7.11-7.16(d，1H，＝CH)，7.33-7.37(d，2H，Ph-H)，7.68-7.71(d，2H，Ph-H)，7.77-7.80(d，1H，＝CH)。

¹³C NMR(DMSO-d₆100MHz) delta 192.53, 151.02, 140.27, 132.53, 127.42, 126.57, 122.23, 80.90, 72.15, 69.59, 69.19, 33.66, 23.31. Example 9

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.2405g (1.3mmol) of 4-bromobenzaldehyde is added into the reaction system, the mixture is ground for 5 to 10min at room temperature, and TLC is used for monitoring until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product. The structural characterization data for the product is: IR (KBr) v 3094cm^-1(-CH＝)，1649cm^-1(C＝O)，1580cm^-1(C＝C)，1523cm^-1，1451cm^-1(Ar，Fc)，817cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:4.24(s，5H，Fc-H)，4.53(s，2H，Fc-H)，4.83(s，2H，Fc-H)，7.11-7.13(d，1H，＝CH)，7.29-7.31(d，2H，Ph-H)，7.55-7.58(d，2H，Ph-H)，7.74-7.78(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.42，138.99，133.78，133.19，131.68，128.94，124.02，122.87，79.97，72.44，69.66，69.26。

Example 10

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1586g (1.3mmol) of 4-hydroxybenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The structural characterization data for the product is: IR (KBr) v 3450cm^-1(-OH)，3089cm^-1(-CH＝)，1645cm^-1(C＝O)，1569cm^-1(C＝C)，1533cm^-1，1441cm^-1(Ar，Fc)，817cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:4.23(s，5H，Fc-H)，4.45(s，2H，Fc-H)，4.73(s，2H，Fc-H)，7.12-7.15(d，1H，＝CH)，7.27-7.31(d，2H，Ph-H)，7.45-7.48(d，2H，Ph-H)，7.64-7.68(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:191.42，138.99，133.68，133.09，130.68，128.84，124.12，122.77，78.97，71.44，69.66，69.26。

Example 11

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1586g (1.3mmol) of 2-hydroxybenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

Structure of the productThe characterization data are: IR (KBr) v 3440cm^-1(-OH)，3087cm^-1(-CH＝)，1648cm^-1(C＝O)，1564cm^-1(C＝C)，1543cm^-1，1448cm^-1(Ar，Fc)，741cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:4.24(s，5H，Fc-H)，4.45(s，2H，Fc-H)，4.63(s，2H，Fc-H)，7.12-7.15(d，1H，＝CH)，7.23-7.31(d，1H，Ph-H)，7.45-7.48(d，2H，Ph-H)，7.75-7.78(d，1H，Ph-H)7.64-7.68(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.42，137.99，132.68，132.09，130.68，127.84，125.12，123.77，79.97，71.44，69.66，69.26。

Example 12

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1937g (1.3mmol) of 4-N, N dimethylaminobenzaldehyde is added into the reaction system, grinding is carried out for 5-10min at room temperature, and TLC monitoring is carried out until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The structural characterization data for the product is: : IR (KBr) v 3085cm^-1(-CH＝)，2968cm^-1，1378cm^-1(-CH₃)，1650cm^-1(C＝O)，1582cm^-1(C＝C)，1523cm^-1，1442cm^-1(Ar，Fc)，817cm^-1(Ar-H)。

¹H NMR(DMSO-d₆，400MHz)δ:1.31(s，6H，-CH₃)，2.98(m，1H，-CH)，4.34(s，5H，Fc-H)，4.50(s，2H，Fc-H)，4.92(s，2H，Fc-H)，7.15-7.17(d，1H，＝CH)，7.32-7.36(d，2H，Ph-H)，7.67-7.71(d，2H，Ph-H)，7.75-7.80(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.55，151.22，140.32，132.73，127.49，125.57，124.23，80.50，74.15，69.29，69.09，33.36，23.39。

Example 13

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1391g (1.3mmol) of 4-pyridinecarboxaldehyde is added into the reaction system, the mixture is ground for 5-10min at room temperature, and TLC is used for monitoring until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The structural characterization data for the product is: IR (KBr) v 3092cm^-1(-CH＝)，1649cm^-1(C＝O)，1580cm^-1(C＝C)，1572cm^-1，1451cm^-1(Ar，Fc)。

¹H NMR(DMSO-d₆，400MHz)δ:4.24(s，5H，Fc-H)，4.63(s，2H，Fc-H)，4.93(s，2H，Fc-H)，7.01-7.03(d，1H，＝CH)，7.09-7.13(d，1H，Py-H)，7.25-7.28(d，1H，Py-H)，7.64-7.78(m，2H，Py-H)，7.48-7.50(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.72，153.09，149.78，138.19，136.68，136.41，128.04，125.02，123.87，79.97，72.44，69.66，69.26。

Example 14

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; adding 0.1248g (1.3mmol) of 2-furaldehyde into the reaction system, grinding for 5-10min at room temperature, and monitoring by TLC until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

Knot of productThe characterization data are: IR (KBr) v 3108cm^-1(-CH＝)，1647cm^-1(C＝O)，1576cm^-1(C＝C)，1549cm^-1，1441cm^-1(Ar，Fc)。

¹H NMR(DMSO-d₆，400MHz)δ:4.14(s，5H，Fc-H)，4.53(s，2H，Fc-H)，4.83(s，2H，Fc-H)，6.82-6.86(d，1H，＝CH)，7.02-7.08(d，1H，Thy-H)，7.29-7.30(m，1H，Thy-H)，7.31-7.35(d，1H，Thy-H)，7.81-7.85(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:191.02，140.01，132.38，130.81，128.04，127.42，126.57，80.97，73.44，69.66，69.26。

Example 15

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1456g (1.3mmol) of 2-thiophenecarboxaldehyde is added into the reaction system, the mixture is ground for 5-10min at room temperature, and TLC is used for monitoring until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product.

The structural characterization data for the product is: IR (KBr) v 3102cm^-1(-CH＝)，1649cm^-1(C＝O)，1580cm^-1(C＝C)，1552cm^-1，1451cm^-1(Ar，Fc)。

¹H NMR(DMSO-d₆，400MHz)δ:4.24(s，5H，Fc-H)，4.63(s，2H，Fc-H)，4.93(s，2H，Fc-H)，6.92-6.96(d，1H，＝CH)，7.09-7.13(d，1H，Thy-H)，7.29-7.30(m，1H，Thy-H)，7.34-7.37(d，1H，Thy-H)，7.91-7.95(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.02，140.09，132.83，130.91，128.04，127.42，125.57，79.97，72.44，69.66，69.26。

Example 16

0.2508g (1.1mmol) of acetyl ferrocene and 0.0279g (0.11mmol) of iodine are added into a mortar, ground and mixed uniformly; 0.1456g (1.3mmol) of 3-thiophenecarboxaldehyde is added into the reaction system, the mixture is ground for 5-10min at room temperature, and TLC is used for monitoring until the reaction is finished; after the reaction is completed, adding a sodium thiosulfate solution into the reaction system, washing, filtering, washing with water, and drying to obtain a crude product. The structural characterization data for the product is: IR (KBr) v 3101cm^-1(-CH＝)，1652cm^-1(C＝O)，1579cm^-1(C＝C)，1553cm^-1，1449cm^-1(Ar，Fc)。

¹H NMR(DMSO-d₆，400MHz)δ:4.25(s，5H，Fc-H)，4.63(s，2H，Fc-H)，4.89(s，2H，Fc-H)，6.91-6.96(d，1H，＝CH)，7.05-7.13(d，1H，Thy-H)，7.28-7.31(m，1H，Thy-H)，7.33-7.37(d，1H，Thy-H)，7.89-7.95(d，1H，＝CH)。

¹³C NMR(DMSO-d₆，100MHz)δ:192.03，140.07，132.83，130.91，128.04，127.42，125.57，79.97，72.44，69.66，69.26。

Ultraviolet visible absorption of different metal ions by 1-phenyl-3-ferrocenyl ketene.

Using the freshly prepared 1-phenyl-3-ferrocenylenone with DMF: H₂O1: 1 configuration 1 × 10^-4And (4) mol/L of the solution to be detected. Mixing AlCl₃，SnCl₂，BaCl₂，CuCl₂，MnCl₂，FeCl₂，LiCl，CaCl₂，KCl，FeCl₃，CoCl₂1X 10 arrangement using ultrapure water^-2mol/L. Accurately measuring 3mL of the solution to be measured in 12 sample tubes with a pipette gun with a range of 1000 μ L, reserving one sample tube as a blank reference sample, and adding 30 μ L of the rest 11 solutions with a pipette gun with a range of 20 μ LThe 11 kinds of test metal ion solutions are subjected to ultrasonic oscillation and standing to uniformly disperse the 12 groups of samples, and then the ultraviolet visible absorption spectrum of the liquid to be tested is tested. All compounds have a certain UV absorption, which contains an enone structure. As shown in FIG. 7, Fe was added³⁺After the ions are added, the absorption intensity of the absorption peak is enhanced and red shift occurs, and the ultraviolet absorption is not obviously changed after other metal ions are added. Shows that 1-phenyl-3-ferrocenyl ketene can obviously identify Fe³⁺Ions, indicating that the 1-phenyl-3-ferrocenyl ketene may be combined with Fe³⁺The ions are complexed.

Ultraviolet visible absorption of different metal ions by 1- (2-hydroxy) phenyl-3-ferrocenyl ketene

Using the freshly prepared 1- (2-hydroxy) phenyl-3-ferrocenylenone with DMF: h₂O1: 1 configuration 1 × 10^{- 4}And (4) mol/L of the solution to be detected. Mixing AlCl₃，SnCl₂，BaCl₂，CuCl₂，MnCl₂，FeCl₂，LiCl，CaCl₂，KCl，FeCl₃，CoCl₂1X 10 arrangement using ultrapure water^-2mol/L. Accurately measuring 3mL of the solution to be tested in 12 sample tubes by using a pipette with the range of 1000 mu L, reserving one sample as a blank reference sample, adding 30 mu L of the 11 test metal ion solutions into the other 11 solutions to be tested by using a pipette with the range of 20 mu L, ultrasonically oscillating the 12 samples, standing to uniformly disperse the 12 samples, and testing the ultraviolet visible absorption spectrum of the solution to be tested. All compounds have a certain UV absorption, which contains an enone structure. As shown in FIG. 8, Fe was added³⁺After the ions are added, the absorption intensity of the absorption peak is enhanced and red shift occurs, and the ultraviolet absorption is not obviously changed after other metal ions are added. The 1- (2-hydroxy) phenyl-3-ferrocenyl ketene can obviously identify Fe³⁺Ions, which indicate that the 1- (2-hydroxy) phenyl-3-ferrocenyl ketene may be possibly combined with Fe³⁺The ions are complexed.

The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.