CN117886858A - Ammonium phosphate compound and preparation method and application thereof - Google Patents

Ammonium phosphate compound and preparation method and application thereof Download PDF

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CN117886858A
CN117886858A CN202311776452.4A CN202311776452A CN117886858A CN 117886858 A CN117886858 A CN 117886858A CN 202311776452 A CN202311776452 A CN 202311776452A CN 117886858 A CN117886858 A CN 117886858A
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compound
ammonium phosphate
reaction
phosphate compound
chiral
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熊小东
吴志鹏
陈智煌
杜雪
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Nanchang University
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Abstract

The invention discloses an ammonium phosphate compound, a preparation method and application thereof, and belongs to the field of organic chemistry. The invention provides a method for preparing ammonium phosphate compound by reacting phosphoric acid compound and amine compound; the ammonium phosphate compound provided by the invention can be used as a catalyst for halogenation reaction to obtain halogenated compounds with various functional groups, and has the advantages of high yield and high optical purity; the preparation method of the ammonium phosphate compound provided by the invention is simple to operate and high in yield; meanwhile, when the ammonium phosphate compound is used as a catalyst in the halogenation reaction, the conditions are mild, the operation is simple and convenient, the cost is lower, the yield is high, the environment is friendly, and the industrial production is facilitated.

Description

Ammonium phosphate compound and preparation method and application thereof
Technical Field
The invention relates to the field of organic chemistry, in particular to an ammonium phosphate compound, a preparation method and application thereof.
Background
The halogenide is an important organic compound, is widely applied to medicines, natural products, dyes, fragrances and pesticides, can be used as an important chemical intermediate, and can be used for constructing molecules with complex structures through metal-catalyzed coupling reaction, nucleophilic substitution reaction, free radical reaction and the like. In addition, fluorine atom or chlorine atom group is introduced into the drug molecule, so that the lipophilicity of the molecule can be increased, the permeability of the lipid membrane can be improved, the biological activity of the drug molecule can be improved, and the halogenation reaction can be applied to the discovery of new drugs. Therefore, the synthesis of halogen compounds has received a great deal of attention in the fields of pharmaceutical chemistry and organic synthetic chemistry, and the development of efficient halogenation methods has become one of the research hotspots in the field of organic chemistry.
Ammonium salt catalyzed halogenation reactions have been extensively studied. In 2004, asymmetric synthesis of iodolactone is realized by using cinchona alkaloid salt as a catalyst and adopting enantioselectivity of 10-42% ee for the first time, but serious side reactions exist, the yield is low, and the enantioselectivity is low, but the pioneering work opens the gates of research on asymmetric halogenation reaction catalyzed by quaternary ammonium salt phase transfer (J.org.chem.2004, 69, 2874), and the reaction formula is shown as follows:
with the application of quaternary ammonium salt phase transfer catalysis in iodination reaction research, new asymmetric halogenation reaction types have also been developed. 2013 first appears that cinchona alkaloid salt is used as a quaternary ammonium salt catalyst, indenone is firstly converted into enol type anions under alkaline conditions, then a key intermediate is formed with chiral ammonium ions, and then the key intermediate reacts with a chlorinating reagent NCS to generate chiral alpha-chlorinated products (Tetrahedron Lett.2013, 54, 2623), and the reaction formula is shown as follows:
2022 found that an α -position asymmetric chlorination of esters was achieved under weak base conditions using a spiro ammonium salt as a catalyst, and α -chloro esters (ACS org. Inorg. Au 2022,2, 34) were synthesized in moderate yields and excellent enantioselectivity, as shown below:
although the asymmetric halogenation reaction catalyzed by ammonium salts has been greatly progressed, the existing methods still have a number of problems including low yield, poor enantioselectivity control and reaction efficiency, single reaction type and substrate structure, high requirements on reaction conditions, difficult catalyst recovery and the like.
Therefore, a new solution is needed to improve the above problems.
Disclosure of Invention
The invention aims to provide an ammonium phosphate compound and a preparation method and application thereof, and solve the problems of low yield, low enantioselectivity control and reaction efficiency, single reaction type and substrate structure, high reaction condition requirement, difficult catalyst recovery and the like in the prior art.
In one aspect, the invention provides an ammonium phosphate compound, which is characterized in that the chemical structural formula is shown as formula I:
wherein the R group comprises one of an alkyl group and an aryl group; the R groups are independent of each other or form a ring;
R 1 、R 2 and R is 3 The radicals independently of one another include one of hydrogen, alkyl, aryl; the R is 1 、R 2 、R 3 The radicals are independent of each other or any two of them form a ring;
said R, R 1 、R 2 、R 3 The groups include, independently of each other, chiral substituents and racemic substituents.
In a second aspect, the invention provides a preparation method of the ammonium phosphate compound, which is characterized in that under a first solvent, phosphoric acid compounds II and amine compounds III react to generate ammonium phosphate compounds I:
wherein the R group comprises one of an alkyl group and an aryl group; the R groups are independent of each other or form a ring;
R 1 、R 2 and R is 3 The radicals independently of one another include one of hydrogen, alkyl, aryl; the R is 1 、R 2 、R 3 The radicals are independent of each other or any two of them form a ring;
said R, R 1 、R 2 、R 3 The groups include, independently of each other, chiral substituents and racemic substituents.
Optionally, the first solvent comprises dichloromethane and dichloroethane.
Optionally, the phosphoric acid compound comprises a chiral compound and a racemic compound.
Optionally, the amine compound includes chiral compounds and racemic compounds.
In a third aspect, the present invention provides the use of the ammonium phosphate compound as a catalyst in a halogenation reaction.
Alternatively, the molar ratio of the ammonium phosphate compound to the reaction substrate is in the range of (1:10) to 1000.
Optionally, the reaction time is 0.5-124h; the reaction temperature is-20-50 ℃.
Optionally the second solvent used in the reaction is an aprotic solvent including toluene, carbon tetrachloride, n-hexane, cyclohexane, n-pentane, n-heptane.
In a fourth aspect, the present invention provides the use of said ammonium phosphate compound in the preparation of a halogenated reagent.
Alternatively, the use includes fluorogenic agents, chlorinated agents, brominated agents, iodinated agents, seleno agents.
The beneficial effects of the invention include:
(1) The invention provides a preparation method of ammonium phosphate compound, which has wide raw material selection and convenient and quick reaction operation;
(2) The ammonium phosphate compound provided by the invention can be used as a catalyst in a halogenation reaction to obtain halogenated compounds with high yield and high enantioselectivity;
(3) The ammonium phosphate catalyst provided by the invention has low usage amount, can be recycled, and has the advantages of cost saving, high efficiency and strong practicability;
(4) The halogenation reaction catalyzed by the ammonium phosphate salt provided by the invention has the advantages of high yield, low cost, simple operation and the like; has good industrialization prospect.
Detailed Description
The invention will be further illustrated by the following examples.
In one aspect, an embodiment of the present invention provides an ammonium phosphate compound, which is characterized in that the chemical structural formula is shown in formula I:
wherein the R group comprises one of an alkyl group and an aryl group; the R groups are independent of each other or form a ring;
R 1 、R 2 and R is 3 Base phaseIndependently of each other, one of hydrogen, alkyl, aryl; the R is 1 、R 2 、R 3 The radicals are independent of each other or any two of them form a ring;
said R, R 1 、R 2 、R 3 The groups include, independently of each other, chiral substituents and racemic substituents.
In a second aspect, an embodiment of the present invention provides a method for preparing the ammonium phosphate compound, which is characterized in that in a first solvent, the following reaction occurs between a phosphoric acid compound II and an amine compound III to generate an ammonium phosphate compound I:
wherein the R group comprises one of an alkyl group and an aryl group; the R groups are independent of each other or form a ring;
R 1 、R 2 and R is 3 The radicals independently of one another include one of hydrogen, alkyl, aryl; the R is 1 、R 2 、R 3 The radicals are independent of each other or any two of them form a ring;
said R, R 1 、R 2 、R 3 The groups include, independently of each other, chiral substituents and racemic substituents.
Optionally, the first solvent comprises dichloromethane and dichloroethane.
Optionally, the phosphoric acid compound comprises a chiral compound and a racemic compound.
Optionally, the amine compound includes chiral compounds and racemic compounds.
In a third aspect, the embodiment of the invention provides an application of an ammonium phosphate compound shown in a formula I as a catalyst in halogenation reaction.
In some embodiments, the molar ratio of the ammonium phosphate compound to the reaction substrate as a halogenation catalyst is in the range of (1:10) to 1000.
In some embodiments, the reaction time is from 0.5 to 124 hours; the reaction temperature is-20-50 ℃.
In some embodiments, the solvent used in the reaction is an aprotic solvent, including at least one of halogenated hydrocarbons, alkanes, aromatic hydrocarbons, ethers.
Specifically, the halogenated hydrocarbon includes carbon tetrachloride and methylene chloride.
Specifically, the alkane includes n-hexane, cyclohexane, n-pentane and n-heptane.
Specifically, the aromatic hydrocarbon includes toluene and xylene.
Specifically, the ether compound includes diethyl ether and tetrahydrofuran.
In a fourth aspect, embodiments of the present invention provide an application of the ammonium phosphate compound in preparing a halogenated reagent.
In particular, the applications include fluoro agents, chloro agents, bromo agents, iodo agents, seleno agents.
Specifically, the fluoro reagent includes Selectfluor.
Specifically, the chlorinating agent comprises dichloro hydantoin and 1, 3-dichloro-5, 5-diphenyl hydantoin.
Specifically, the brominating reagent comprises N-bromosuccinimide, dibromohydantoin and N-bromophthalimide.
Specifically, the iodination reagent comprises N-iodinated succinimide, diiodohydantoin and N-iodophthalimide.
Specifically, the seleno reagent comprises N- (phenylseleno) phthalimide.
Specifically, when the halogenated reagent is applied, the molar ratio of the reaction substrate to the halogenated reagent is 1:1-5.
Phosphoric acid is used in the examples of the present invention as a commercially available or chemical synthesis by the methods mentioned in the following two documents: (1) org.biomol.chem.,2018, 16, 4753-4777; (2) chem.rev.2014, 114, 9047-9153.
Example 1
The embodiment 1 of the invention provides a preparation method of an ammonium phosphate compound I-1, the reaction formula is shown as follows, and the preparation method comprises the following steps:
s1, 1.5g (2 mmol) of phosphoric acid compound II-1 and 30mL of methylene dichloride are taken and placed in a reaction bottle, 0.42g (3 mmol) of 2, 6-tetramethylpiperidine III-1 is added for reaction for 24 hours at 25 ℃;
s2, spin-drying the reaction solvent to obtain a pale yellow solid;
s3, washing and filtering the light yellow solid by normal hexane to obtain 1.51g of white solid I-1, wherein the calculated yield is 81%;
the reaction formula for preparing the ammonium phosphate salt compound I-1 in the embodiment 1 of the invention is shown as follows:
the white solid obtained in the step S3 is characterized by nuclear magnetic resonance and identified as a target compound ammonium salt I-1, and the data are as follows:
1 H NMR(400MHz，CDCl 3 )δ8.35(s，1H)，7.85(d，J＝8.0Hz，2H)，7.79(s，2H)，7.38-7.43(s，2H)，7.20-7.26(s，4H)，7.09(d，J＝1.6Hz，2H)，7.01(d，J＝1.6Hz，2H)，2.91-2.99(m，4H)，2.77-2.83(m，2H)，1.50-1.55(m，2H)，1.37-1.39(m，4H)，1.30(d，J＝6.8Hz，12H)，1.23(d，J＝6.8Hz，6H)，1.19(d，J＝6.8Hz，6H)，1.14(d，J＝6.8Hz，6H)，1.04(d，J＝12.0Hz，12H)，0.90(d，J＝6.8Hz，6H)；
13 C NMR(100MHz，CDCl 3 )：δ148.3，148.2，147.6，147.5，133.6，133.1，133.0(2)，132.0，130.4，128.0，127.5，125.5，124.6，122.9，122.8，121.1，120.0，55.4，35.3，34.5，31.7，30.9，30.8，27.6，27.5，26.4，25.2，24.6，24.3，24.1，23.3，22.8，16.3，14.3.
31 P NMR(130MHz，CDCl 3 )δ3.44.
example 2
Example 2 of the present invention provides a process for preparing ammonium phosphate compound I-2, which is different from example 1 in that 2, 6-tetramethylpiperidine is replaced with dicyclohexylamine III-2 of the same molar mass in step S1; 1.68g of white solid I-2 are obtained in step S3, calculated yield 90%;
the reaction scheme of this example 2 is shown below:
the white solid obtained in example 2 was characterized by nuclear magnetic resonance and identified as the ammonium salt of the target compound I-2 as follows:
1 H NMR(400MHz，CDCl 3 )δ8.82(s，2H)，7.87(d，J＝8.4Hz，2H)，7.81(s，2H)，7.42(d，J＝7.6Hz，2H)，7.23-7.32(m，4H)，7.08(s，2H)，7.02(s，2H)，2.89-3.02(m，4H)，2.72-2.79(m，2H)，2.61-2.70(m，2H)，1.54-1.82(m，10H)，1.29(J＝6.8Hz，12H)，1.15-1.23(m，20H)，1.03-1.12(m，6H)，0.93(J＝76.8Hz，6H)，0.85-0.91(m，2H)；
13 C NMR(100MHz，CDCl 3 )：δ148.2，148.1，147.8，147.6，133.4，133.2(2)，132.9，131.7，130.4，128.1，127.5，125.6，124.7，122.9(2)，120.6，119.9，53.2，34.4，31.0，30.9，29.9，28.9，26.8，25.3，24.8，24.7，24.5，24.1，23.4，23.3.
31 P NMR(130MHz，CDCl 3 )δ5.22.
example 3
Example 3 of the present invention provides a method for producing an ammonium phosphate compound, which is different from example 2 in that the phosphoric acid II-1 in step S1 is replaced with a phosphoric acid II-2 of the same molar mass, and other conditions and steps are kept the same; 1.77g of white solid I-3 are obtained in step S3, calculated yield 94%;
the reaction formula for preparing the ammonium phosphate salt compound I-3 in the embodiment 3 of the invention is shown as follows:
the white solid obtained in example 3 was characterized by nuclear magnetic resonance and identified as the ammonium salt of the target compound I-3 as follows:
1 H NMR(400MHz，CDCl 3 )δ8.82(s，2H)，7.01(s，2H)，6.95(s，2H)，6.87(s，2H)，2.95-3.04(m，2H)，2.64-2.92(m，13H)，2.44-2.58(m，3H)，2.23-2.31(m，2H)，1.77-1.87(m，8H)，1.65-1.74(m，8H)，1.26(d，J＝7.2Hz，12H)，1.14-1.21(m，20H)，1.01-1.06(m，4H)，0.87-0.92(m，8H)；
13 C NMR(100MHz，CDCl 3 )：δ147.9，147.5，147.1，146.2，146.1，135.9，133.8，132.1，132.0，129.3，129.2，128.1，120.5，119.8，53.0，34.3，31.7，30.7，30.6，29.5，29.4，29.0，27.9，26.7，25.1，24.8(2)，24.7，24.5，24.1，23.6，23.5，23.2(2)，22.8，14.3.
31 P NMR(130MHz，CDCl 3 )δ2.32.
example 4
Example 4 of the present invention provides a method for producing an ammonium phosphate compound, which is different from example 2 in that the phosphoric acid II-1 in step S1 is replaced with a phosphoric acid II-3 of the same molar mass, and other conditions and steps are kept the same; step S3 gave 0.67g of white solid I-4 in 78% yield;
the reaction formula for preparing the ammonium phosphate salt compound I-4 in the example 4 of the present invention is shown as follows:
the white solid obtained in example 4 was characterized by nuclear magnetic resonance and identified as the ammonium salt of the target compound I-4 as follows:
1 H NMR(400MHz，CDCl 3 )：δ9.12(s，2H)，7.14-7.19(m，8H)，6.92-6.97(m，2H)，2.71-2.77(m，2H)，1.85-1.89(m，4H)，1.60-1.64(m，4H)，1.45-1.49(m，2H)，1.32-1.42(m，4H)，0.91-1.10(m，6H).
example 5
Example 5 of the present invention provides a process for producing an ammonium phosphate compound, which is different from example 4 in that dicyclohexylamine III-2 in step S1 is replaced with amine III-2 (diisopropylethylamine) of the same molar mass, and other conditions and steps are kept the same; 1.11g of pale yellow oily liquid I-5 are obtained in the step S3, and the calculated yield is 98%;
the reaction formula for preparing the ammonium phosphate compound I-5 in the example 5 of the present invention is shown below:
the pale yellow oily liquid obtained in example 5 was characterized by nuclear magnetic resonance and identified as the ammonium salt of the objective compound I-5, as follows:
1 H NMR(400MHz，CDCl 3 )：δ10.92(s，1H)，7.12-7.23(m，8H)，6.90-6.93(m，2H)，3.32-3.36(m，2H)，2.76-2.83(m，2H)，1.15-1.22(m，15H).
example 6
The embodiment 6 of the invention provides an application of an ammonium phosphate salt compound I-1 in catalyzing asymmetric bromo-half pinacol rearrangement reaction of a diene compound, which comprises the following steps:
d1, 0.2g (1 mmol) of the binaphthyl compound 1, 44.7mg (0.05 mmol) of the ammonium phosphate salt compound I-1 prepared in example 1 and 40mL of cyclohexane were placed in a reaction flask, 195.6mg (1.1 mmol) of N-bromosuccinimide (NBS) was added thereto, and reacted at 25℃for 12 hours;
d2, 20mL of saturated sodium sulfite solution, 60mL of ethyl acetate are added, and the organic layer is washed 2 times with 25mL of water;
d3, after washing, drying over anhydrous sodium sulfate, recovering ethyl acetate, column chromatography (PE/ea=20:1) to give 198.8mg of rearrangement product 2, calculated yield 71%;
the reaction formula of the application of the ammonium phosphate salt compound I-1 in the catalysis of the asymmetric bromo-half pinacol rearrangement reaction of the diene compound in the embodiment 6 of the invention is as follows:
the enantiomeric excess value (ee) was determined from the chiral high pressure liquid phase, and the ee value was 91%;
c, performing nuclear magnetic resonance characterization on the rearrangement product 2 obtained in the step D3, and identifying the rearrangement product as a target compound 2;
1 H NMR(400MHz，CDCl 3 )δ 1 H NMR(400MHz，CDCl 3 )：δ9.67(s，1H)，7.38-7.43(m，2H)，7.32-7.36(m，3H)，6.04(d，J＝2.8Hz，1H)，5.97(d，J＝2.8Hz，1H)，2.19-2.26(m，1H)，2.11(dd，J＝4.8，12.0Hz，1H)，1.36-1.46(m，2H)，1.14-1.34(m，2H)，0.93(t，J＝7.2Hz，3H)；
13 C NMR(100MHz，CDCl 3 )：δ196.4，137.1，134.1，129.0，128.3，128.2，121.6，65.9，31.8，27.1，23.3，14.1.
example 7
Example 7 of the present invention provides the use of ammonium phosphate compound I-3 in the catalytic asymmetric bromo-semipinacol rearrangement of allylic compounds, differing from example 6 in that step D1 is: 0.2g (1 mmol) of allyl alcohol 3, 47.1mg (0.05 mmol) of ammonium salt I-3 and 40mL of n-hexane/carbon tetrachloride (volume ratio 1:10) are placed in a reaction flask; 195.6mg (1.1 mmol) of NBS was added and reacted at 25℃for 120 hours; the steps D2 and D3 are consistent, 222.4mg of rearranged product 4 is obtained through column chromatography (PE/EA=20:1), and the yield is 80%;
the reaction formula of the application of the ammonium phosphate compound I-3 in the asymmetric bromo-half pinacol rearrangement reaction of the allyl alcohol compound in the embodiment 7 of the present invention is shown as follows:
the enantiomeric excess value (ee) was determined from the chiral high pressure liquid phase, and the ee value was determined to be 96%;
the rearrangement product 4 obtained in the step D3 is identified as a target compound 4 through nuclear magnetic resonance characterization, and the data are shown as follows:
1 H NMR(400MHz，CDCl 3 )：δ7.04-7.07(m，2H)，6.88-6.90(m，2H)，3.94(dd，J＝3.6，12.0Hz，1H)，3.14-3.25(m，1H)，2.61-2.68(m，1H)，2.44-2.54(m，2H)，2.34-2.40(m，1H)，2.13-2.21(m，2H)，2.05-2.11(m，1H)，1.87-1.97(m，1H)，1.63-1.73(m，1H)；
13 C NMR(100MHz，CDCl 3 )：δ217.3，138.5，135.8，129.4，127.5，127.0，126.9，56.8，56.2，40.0，38.9，30.1，29.7，19.9.
example 8
Example 8 of the present invention provides the use of ammonium phosphate compound I-2 in the catalytic asymmetric bromocyclization of a tryptamine compound, differing from example 6 in that step D1 is: 318mg (1 mmol) of the tryptamine compound 5, 46.7mg (0.05 mmol) of the ammonium salt I-2 and 40mL of a mixed solution of n-hexane and carbon tetrachloride (volume ratio is 2:1) are placed in a reaction bottle, 195.6mg (1.1 mmol) of NBS is added, and the mixture is reacted for 2 hours at 25 ℃;
step D2 and D3 are identical, 360.4mg of bromocyclized product 6 is obtained by column chromatography (PE/ea=20:1), the calculated yield is 91%;
the reaction formula of the application of the ammonium phosphate compound I-2 in the asymmetric bromocyclization reaction of the tryptamine compound in the embodiment 8 of the invention is shown as follows:
the enantiomeric excess value (ee) was determined from the chiral high pressure liquid phase, and the ee value was determined to be 96%;
the bromocyclized product 6 obtained in step D3 was characterized by nuclear magnetic resonance and identified as the target compound 6 as shown below:
1 H NMR(400MHz，CDCl 3 )：δ7.64(d，J＝8.0Hz，1H)，7.37(d，J＝7.6Hz，1H)，7.31(t，J＝7.8Hz，1H)，7.11(t，J＝7.6Hz，1H)，6.39(s，1H)，3.80-3.78(m，1H)，3.74(s，3H)，2.91-2.82(m，2H)，2.79-2.71(m，1H)，1.59(s，9H)；
13 C NMR(100MHz，CDCl 3 )：δ154.9，152.3，142.1，132.5，130.7，124.4，123.8，117.5，84.1，82.3，62.2，52.9，46.4，41.2，28.4.
example 9
Example 9 of the present invention provides the use of ammonium phosphate compound I-2 in the catalysis of the reaction in the asymmetric bromocyclization of a tryptamine compound, comprising the steps of:
1.59g (5 mmol) of the tryptamine compound 5, 46.7mg (0.05 mmol) of the ammonium salt I-2 and 100mL of a mixed solution of n-hexane and carbon tetrachloride (volume ratio is 2:1) are placed in a reaction bottle, 978mg (5.5 mmol) of NBS is added, and the mixture is reacted for 2 hours at 25 ℃;
30mL of saturated sodium sulfite solution was added, 120mL of ethyl acetate was added, and the organic layer was washed 2 times with 30mL of water;
column chromatography (PE/ea=20:1) gives 1.88g of bromocyclized product 6, calculated as 95%;
the reaction formula of the application of the ammonium phosphate compound I-2 in the asymmetric bromocyclization reaction of the tryptamine compound in the embodiment 9 of the invention is shown as follows:
the enantiomeric excess (ee) was determined from the chiral high pressure liquid phase and found to be 97%.
Example 10
The example 10 of the present invention provides a method for recycling the ammonium phosphate compound I-2 used in the example 9 after passing through the column, performing secondary catalysis by using the ammonium phosphate compound I-2, and the condition steps are the same as those in the example 9; the bromocyclized product 6 obtained in step D3 is 1.91g, calculated yield is 97%; the ee value is 96%;
the ammonium phosphate compound I-2 can be recycled to catalyze asymmetric bromocyclization reaction for the second time, and the yield and ee value of the product obtained by the reaction have no obvious difference from those of the example 9.
Example 11
Example 11 of the present invention provides the use of ammonium phosphate compound I-2 in the catalytic asymmetric bromocyclization of a color alcohol compound, differing from example 6 in that step D1 is: 261mg (1 mmol) of tryptamine compound 7, 46.7mg (0.05 mmol) of ammonium salt I-2 and 40mL of n-hexane are placed in a reaction flask; 195.6mg (1.1 mmol) of NBS was added and reacted at 25℃for 24 hours;
step D2 and step D3 are consistent, 338mg of bromocyclized product 8 is obtained through column chromatography (PE/ea=20:1), and the calculated yield is 99%;
the reaction formula of the application of the ammonium phosphate compound I-2 in the asymmetric bromocyclization reaction of the color alcohol compound in the embodiment 11 of the invention is shown as follows:
the enantiomeric excess value (ee) was determined from the chiral high pressure liquid phase, and the ee value was 99%;
the obtained bromocyclized product 8 is characterized by nuclear magnetic resonance and identified as a target compound 8, and the data are shown as follows:
1 H NMR(400MHz，CDCl 3 )：δ7.83(s，1H)，7.40(d，J＝7.6Hz，1H)，7.29(d，J＝7.6Hz，1H)，7.07(dt，J＝0.9Hz，7.5Hz，1H)，6.19(s，1H)，4.01-3.97(m，1H)，3.51-3.45(m，1H)，2.93-2.85(m，1H)，2.81-2.77(m，1H)，1.60(s，9H)；
13 C NMR(100MHz，CDCl 3 )：δ151.9，141.9，131.7，130.6，124.9，123.8，115.0，100.8，82.2，67.9，61.5，45.1，28.4.
example 12
Example 12 of the present invention provides the use of ammonium phosphate compound I-2 in the catalytic asymmetric iodination of a color alcohol compound, differing from example 6 in that step D1 is: 261mg (1 mmol) of tryptamine compound 7, 46.7mg (0.05 mmol) of ammonium salt I-2 and 40mL of n-hexane are placed in a reaction flask; 25.4mg (0.1 mmol) of I are added 2 And 195.6mg (1.1 mmol) NBS, reacted at 25℃for 24h;
d2, D3 steps are identical, and column chromatography (PE/ea=20:1) gives 344mg of iodinated cyclized product 9, calculated yield 89%;
the reaction formula of the application of the ammonium phosphate compound I-2 in the asymmetric iodination cyclization reaction of the color alcohol compound in the embodiment 12 of the invention is shown as follows:
the enantiomeric excess value (ee) was determined from the chiral high pressure liquid phase, and the ee value was 99%;
the obtained iodinated cyclization product 9 is characterized by nuclear magnetic resonance and identified as a target compound 9, and the data are shown as follows:
1 H NMR(400MHz，CDCl 3 )δ7.78(s，1H)，7.39(d，J＝7.6Hz，1H)，7.25-7.21(m，1H)，7.05(t，J＝7.4Hz，1H)，6.28(s，1H)，3.80(t，J＝8.2Hz，1H)，3.42-3.35(m，1H)，2.98-2.86(m，1H)，1.61(s，9H)；
13 C NMR(100MHz，CDCl 3 )：δ152.0，130.0，125.2，124.0，115.0，103.3，82.2，67.4，47.9，28.5.
example 13
Example 13 of the present invention provides the use of ammonium phosphate compound I-3 in the catalytic rearrangement of allylic alcohols with asymmetric seleno-half pinacol, differing from example 6 in that step D1 is: 0.2g (1 mmol) of allyl alcohol 7, 47.1mg (0.05 mmol) of ammonium salt I-3 and 40mL of a mixture of n-hexane and carbon tetrachloride (volume ratio 1:20) are placed in a reaction flask; 304mg (2 mmol) of NPSP were added and reacted at 25℃for 24h;
the steps D2 and D3 are consistent, 288.4mg of rearranged product 10 is obtained through column chromatography (PE/EA=20:1), and the calculated yield is 81%;
the reaction formula of the application of the ammonium phosphate compound I-3 in the asymmetric seleno-half pinacol rearrangement reaction of the allyl alcohol compound in the embodiment 13 of the invention is shown as follows:
the enantiomeric excess value (ee) was determined from the chiral high pressure liquid phase, and the ee value was determined to be 64%;
the resulting rearrangement product 10 was characterized by nuclear magnetic resonance and High Resolution Mass Spectrometry (HRMS) and identified as the target compound 10 as shown below:
1 H NMR(400MHz，CDCl 3 )δ7.58-7.60(m，2H)，7.27-7.31(m，3H)，7.12-7.15(m，2H)，7.07-7.10(m，1H)，6.93-6.95(m，1H)，3.59(dd，J＝3.2，8.0Hz，1H)，3.08-3.16(m，1H)，2.69-2.77(m，1H)，2.49-2.62(m，3H)，2.27-2.39(m，2H)，2.10-2.22(m，3H)；
13 C NMR(100MHz，CDCl 3 )：δ219.5，138.9，136.6，135.0，130.1，129.3(2)，128.2，127.9，126.7，126.6，56.9，47.1，41.7，38.9，28.1，26.5，19.4；
HRMS(ESI)calcd for C 20 H 21 SeO m/z[M+H] + ：357.0752，found：357.0758.
example 14
Example 14 of the present invention provides the use of a catalyst in the asymmetric chlorocyclization of an unsaturated amide compound catalyzed by an ammonium phosphate compound I-3, differing from example 6 in that step D1 is: 315mg (1 mmol) of unsaturated amide 11, 47.1mg (0.05 mmol) of ammonium salt I-3 and 40mL of a mixed solution of n-hexane and carbon tetrachloride (volume ratio 1:20) are placed in a reaction bottle; 216.7mg (1.1 mmol) of DCH was added and reacted at 25℃for 24 hours;
d2, D3 steps are identical, and column chromatography (PE/ea=20:1) gives 338.5mg of chlorocyclized product 12, calculated yield 97%;
the reaction formula of the application of the catalyst in the asymmetric chlorocyclization reaction of the unsaturated amide compound catalyzed by the ammonium phosphate compound I-3 in the embodiment 14 of the invention is shown as follows:
the enantiomeric excess value (ee) was determined from the chiral high pressure liquid phase, and the ee value was 80%;
the obtained chloro-cyclized product 12 was characterized by nuclear magnetic resonance and identified as the target compound 12, and the data are shown below:
1 H NMR(400MHz，CDCl 3 )δ7.92(d，J＝8.0Hz，2H)，7.60(d，J＝8.0Hz，2H)，7.41-7.42(m，4H)，7.33-7.39(m，1H)，4.51(d，J＝15.2Hz，1H)，4.24(dd，J＝14.8Hz，1H)，3.94(d，J＝12.0Hz，1H)，3.86(d，J＝12.0Hz，1H)；
13 C NMR(100MHz，CDCl 3 )：δ162.3，141.4，131.8，129.9，128.9，128.5，126.5，126.4，125.0，88.0，65.1，51.1.
example 15
Example 15 of the present invention provides the use of catalysis in the bromocyclization reaction of a phosphorated ammonium compound I-4 catalyzed by a tryptamine compound, which differs from example 6 in that step D1 is: 318mg (1 mmol) of the unsaturated amide 11, 21.6mg (0.05 mmol) of ammonium salt I-4 and 20mL of a mixed solution of n-hexane and carbon tetrachloride (volume ratio 2:1) are placed in a reaction bottle; 2195.6mg (1.1 mmol) of NBS was added and reacted at 25℃for 2 hours;
the steps D2 and D3 are consistent, 376.2mg of chlorocyclized product 12 is obtained through column chromatography (PE/EA=20:1), and the calculated yield is 95%.
The reaction formula of the application of the catalyst in the bromocyclization reaction of the ammonium phosphate compound I-4 in the embodiment 15 of the invention is shown as follows:
while embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention described herein is capable of other embodiments and of being practiced or of being carried out in various ways.

Claims (9)

1. An ammonium phosphate compound is characterized in that the chemical structural formula is shown as formula I:
wherein the R group comprises one of an alkyl group and an aryl group; the R groups are independent of each other or form a ring;
R 1 、R 2 and R is 3 The radicals independently of one another include one of hydrogen, alkyl, aryl; the R is 1 、R 2 、R 3 The radicals are independent of each other or any two of them form a ring;
said R, R 1 、R 2 、R 3 The groups include, independently of each other, chiral substituents and racemic substituents.
2. The method for preparing ammonium phosphate compound according to claim 1, wherein in the first solvent, the phosphoric acid compound II and the amine compound III react to form ammonium phosphate compound I:
wherein the R group comprises one of an alkyl group and an aryl group; the R groups are independent of each other or form a ring;
R 1 、R 2 and R is 3 The radicals independently of one another include one of hydrogen, alkyl, aryl; the R is 1 、R 2 、R 3 The radicals are independent of each other or any two of them form a ring;
said R, R 1 、R 2 、R 3 The groups include, independently of each other, chiral substituents and racemic substituents.
3. The method of claim 2, wherein the phosphate compound comprises a chiral compound and a racemic compound.
4. The method of claim 2, wherein the amine compound comprises a chiral compound and a racemic compound.
5. Use of the ammonium phosphate compound according to claim 1 as a catalyst in halogenation reactions.
6. The use according to claim 5, wherein the molar ratio of ammonium phosphate compound to reaction substrate is (1:10) -1000.
7. The use according to claim 5, wherein the reaction time is 0.5-124h; the reaction temperature is-20-50 ℃.
8. The use according to claim 5, wherein the second solvent used in the reaction is an aprotic solvent comprising toluene, carbon tetrachloride, n-hexane, cyclohexane, n-pentane, n-heptane.
9. Use of the ammonium phosphate salt compound according to claim 1 for the preparation of a halogenated reagent.
CN202311776452.4A 2023-12-22 2023-12-22 Ammonium phosphate compound and preparation method and application thereof Pending CN117886858A (en)

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