CN113999129B - Synthesis method of amino acid surfactant containing phenolic hydroxyl group - Google Patents
Synthesis method of amino acid surfactant containing phenolic hydroxyl group Download PDFInfo
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- CN113999129B CN113999129B CN202111391875.5A CN202111391875A CN113999129B CN 113999129 B CN113999129 B CN 113999129B CN 202111391875 A CN202111391875 A CN 202111391875A CN 113999129 B CN113999129 B CN 113999129B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
Abstract
The invention discloses a synthesis method of an amino acid surfactant containing phenolic hydroxyl groups. The method is that benzofuranone compound and amino acid and/or amino acid salt are subjected to oxidation ring-opening-condensation tandem reaction under the action of di-tert-butyl peroxide oxidant, so as to obtain the amino acid surfactant containing phenolic hydroxyl. The amino acid derivative containing phenolic hydroxyl groups synthesized by the method has better bioactivity, better medicinal prospect, and the synthesis has the advantages of lower cost, high yield, simple and convenient operation, no pollution and the like, and meets the industrial production requirements.
Description
Technical Field
The invention relates to a method for synthesizing an amino acid surfactant, in particular to a method for synthesizing a phenolic hydroxyl-containing amino acid surfactant by oxidation ring-opening-condensation tandem reaction of a benzofuranone compound and amino acid and/or amino acid salt, belonging to the technical field of organic synthesis.
Background
The amide compound is an important fine chemical intermediate, and can be widely applied to the fields of pesticides, organic functional materials, medicines and the like. The main method for synthesizing the amide compounds is to ammonify the acyl chloride compounds into the amide compounds, the reaction is required to be carried out under the condition of strong acid or strong alkali, for example, concentrated sulfuric acid, concentrated nitric acid, KOH, DCC, DMAP and the like are adopted as catalytic action, but the esterification reaction methods have a plurality of problems of generating a large amount of byproducts, and the method has the advantages of complex post-treatment, low yield, long reaction time, poor tolerance of functional groups, large environmental pollution and the like, and in addition, a special corrosion-resistant reaction kettle is required in the catalytic esterification reaction process of the concentrated sulfuric acid, high requirements on equipment and great potential safety hazards exist.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a method for synthesizing a phenolic hydroxyl-containing amino acid surfactant by utilizing a benzofuranone compound and amino acid (or salt) to perform an oxidative ring-opening-condensation tandem reaction.
In order to achieve the technical aim, the invention provides a synthesis method of a surfactant containing phenolic hydroxyl amino acid, which comprises the steps of carrying out oxidative ring opening-condensation tandem reaction on benzofuranone compound and amino acid and/or amino acid salt under the action of di-tert-butyl peroxide oxidant to obtain the surfactant containing phenolic hydroxyl amino acid.
As a preferred embodiment, the benzofuranone compound has a structure represented by formula 1:
wherein R is C 8 ～C 18 Is a fatty hydrocarbon group of (a).
The benzofuranone compounds of the invention wherein R may be a saturated aliphatic hydrocarbon group, e.g. C 8 ～C 18 Saturated aliphatic hydrocarbon group, saturated aliphatic hydrocarbon group is C 8 ～C 18 Alkyl chains, which may be straight or branched, such as undecyl, tridecyl, heptadecyl, and the like. R may also be an unsaturated aliphatic hydrocarbon radical, e.g. C 8 ～C 18 Unsaturated fatty hydrocarbon group, unsaturated fatty hydrocarbon group being C 8 ～C 18 The number of alkenyl or alkynyl groups contained in the alkenyl or alkynyl chain is 1 or more, and the position of the alkenyl or alkynyl group is not limited, and the number of alkenyl or alkynyl groups is generally 1, specifically, 7-pentadecenyl or 9-heptadecenyl, and the like.
As a preferred embodiment, the amino acid is at least one of the amino acids commonly known in the art, such as glutamic acid, glycine, alanine, sarcosine, and methyltaurine.
As a preferred embodiment, the amino acid salt is an amino acid salt commonly known in the art, such as at least one of glutamate, glycinate, alaninate, sarcosinate or methyltaurinate. Specific cations in the amino acid salt are potassium ion, sodium ion, TEA ion and the like.
As a preferred embodiment, the benzofuranyl amino acid surfactant has a structure represented by formula 2:
wherein, the liquid crystal display device comprises a liquid crystal display device,
r is C 8 ～C 18 Is a fatty hydrocarbon group of (2);
a is one of the following amino acid groups:
m is hydrogen ion, potassium ion, sodium ion or TEA ion.
As a preferred embodiment, the molar amount of the di-t-butyl peroxide is 25 to 75%, more preferably 40 to 60%, of the molar amount of the benzofuranone compound. The yield of the target product is obviously reduced when the dosage of the di-tert-butyl peroxide is less than 0.5 times of the molar quantity of the benzofuranone compound, the yield of the target product is not obviously improved when the dosage of the tert-butyl peroxide oxidant is more than 0.5 times of the molar quantity of the benzofuranone compound, and the peak value is reached when the dosage of the tert-butyl peroxide oxidant is 0.5 times of the molar quantity of the benzofuranone compound.
As a preferred embodiment, the oxidative ring-opening-condensation tandem reaction conditions are: reacting for 8-16 h at 120-160 ℃. The ring-opening-condensation tandem reaction between benzofuranone compound and sodium glutamate has obviously improved yield of target product along with the increase of the reaction temperature and the extension of the reaction time, but when the reaction temperature is increased to more than 140 ℃, the reaction time exceeds 12 hours, the yield of the target product is not obviously increased, but is slightly reduced, possibly caused by side reaction, so that the reaction temperature is 140 ℃ and the reaction time is 12 hours, which is the optimal reaction condition of the reaction.
As a preferred embodiment, the ring-opening-condensation tandem reaction uses at least one of acetonitrile, toluene, chlorobenzene as a solvent. The reaction can be smoothly carried out in most organic solvents, but when chlorobenzene, acetonitrile and toluene are used as solvents, a higher target product can be obtained, and when acetone and the like are used, the reaction can be smoothly carried out, but the yield of the target product is lower. Toluene is the reaction solvent for the reaction that is optimal.
The specific reaction principle which may exist for the oxidative ring-opening-condensation reaction between benzofuranones according to the invention and amino acids and/or amino acid salts: under the heating condition, the peroxy bond of the di-tert-butyl peroxide is broken to generate two molecules of tert-butyloxy free radicals, one molecule of tert-butyloxy free radicals acts on amino groups in amino acid to generate amino free radicals, and the other molecule of tert-butyloxy free radicals acts on benzofuranone compound to break and open internal lipid bonds to form acyl free radicals, and the acyl free radicals are combined with the amino free radicals to form amide bonds, so that the target product is finally obtained.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the synthesis method of the phenolic hydroxyl-containing amino acid surfactant takes the di-tert-butyl peroxide as the oxidant, can realize the synthesis of the benzo phenolic hydroxyl-containing amino acid surfactant under the heating condition, has the characteristics of simple operation, mild condition, high yield, low cost and the like, and is favorable for realizing the industrialized production of the phenolic hydroxyl-containing amino acid surfactant.
The amino acid surfactant containing phenolic hydroxyl has better biological activity and physicochemical property and has greater pharmaceutical value due to the introduction of active phenolic hydroxyl.
Detailed Description
So that the manner in which the above recited features, advantages and objects of the present invention can be understood in detail, a more particular description of the invention, briefly summarized below, may be had by reference to embodiments. In the above description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
The reaction materials and catalysts referred to in the following examples are commercially available reagents which are conventional in the market unless otherwise specified.
Condition optimization experiment: taking 2-undecyl-benzofuranone and sodium glutamate as an example to synthesize benzofuranyl amino acid surfactant, optimizing the conditions of oxidant dosage, solvent selection, reaction temperature, time and the like to obtain the optimal reaction conditions, wherein the specific reaction under the optimal reaction conditions is as follows:
to a 10mL reaction tube were added 0.2mmol of 2-undecyl-benzofuranone, 0.2mmol of sodium glutamate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIB (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 90%.
The following experimental groups 1 to 20 are comparative illustrations with the above reactions as standard references:
as can be seen from the above tables, the yields of the target products are significantly reduced when the amount of di-t-butyl peroxide used is less than 0.5 times the molar amount of 2-undecyl-benzofuranone, while the yields of the target products are not significantly improved when the amount of t-butyl peroxide oxidizing agent used is greater than 0.5 times the molar amount of 2-undecyl-benzofuranone.
As can be seen from the above tables, in the experimental groups 1 and 4 to 6, the reaction was smoothly performed in most of the organic solvents, but the target product was obtained higher when chlorobenzene, acetonitrile and toluene were used as solvents, and the target product yield was lower although the reaction was smoothly performed using acetone or the like. Toluene is the reaction solvent for the reaction that is optimal.
As can be seen from the above tables of experimental groups 1 and 7 to 17, the oxidation ring-opening-condensation tandem reaction between 2-undecyl-benzofuranone and sodium glutamate has significantly improved yield of the target product with the increase of the reaction temperature and the extension of the reaction time, but when the reaction temperature is increased to 140 ℃ or more and the reaction time exceeds 12 hours, the increase of the yield of the target product is insignificant and slightly reduced, possibly caused by side reaction, so that the reaction temperature is 140 ℃ and the reaction time is 12 hours, which is the optimal reaction condition for the reaction.
As can be seen from the above table in experimental groups 1 and 18 to 20, the reaction can be smoothly performed by using concentrated sulfuric acid, hydrogen peroxide, m-chloroperoxybenzoic acid and the like, but the reaction effect is far worse than that of di-tert-butyl peroxide.
Examples 1 to 55
The following examples are given under most preferred reaction conditions to examine the effect of different substrates on obtaining the desired product by ring opening-condensation: putting benzofuranone compound, amino acid (or salt), di-tert-butyl peroxide oxidant and solvent into a reaction vessel, reacting for 12 hours in a nitrogen environment at 140 ℃, separating by column after the reaction is completed to obtain a target product, and obtaining specific glutamic acid compounds IIA-IIE, glycine compounds IIIA-IIIC, alanine compounds IVA-IVB, sarcosine compounds VA-VD and methyltaurine compounds VIA-VIC by adopting different benzofuranone derivatives and different amino acid (or salt) through ring opening-condensation, wherein the specific steps are as follows:
wherein R is undecyl, tridecyl, 7-pentadecenyl, heptadecyl, 9-heptadecenyl and other functional groups.
Example 1
To a 10mL reaction tube were added 0.2mmol of 2-undecyl-benzofuranone, 0.2mmol of sodium glutamate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIB (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 90%.
IIB (r=undecyl) structural characterization:
1 H NMR(400MHz,Chloroform-d)δ12.66(s,1H),9.68(s,1H),8.32(s,1H),7.27(d,J＝7.7Hz,1H),7.11(t,J＝7.7Hz,1H),6.86–6.84(m,1H),6.29(d,J＝19.7Hz,1H),4.58–4.55(m,J＝6.8Hz,1H),3.24–3.22(m,1H),2.35–2.33(m,2H),2.08–2.05(m,2H),1.84(q,J＝10.1Hz,1H),1.27–1.24(m,18H),0.88(t,J＝13.2Hz,3H).
13 C NMR(101MHz,CDCl 3 )δ178.0,174.7,170.4,155.2 129.5,127.3,127.0,121.1,115.7,58.7,40.2,33.5,33.1,31.9,31.5,30.5,29.6,29.2,27.5,26.0,22.7,14.1.
example 2
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of potassium glutamate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIC (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 91%.
Example 3
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of sodium glutamate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction, the target compound IIB (r=tridecyl) was obtained by column chromatography separation, and a white powder was obtained in 89% yield.
Example 4
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of potassium glutamate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound IIC (r=tridecyl) was obtained by column chromatography separation, and a white powder was obtained in 91% yield.
Example 5
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of sodium glutamate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIB (r=7-pentadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in a yield of 90%.
Example 6
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of potassium glutamate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIC (r=7-pentadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 92% yield.
Example 7
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=heptadecyl), 0.2mmol of sodium glutamate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction was completed, the target compound IIB (r=heptadecyl) was obtained by separation by column chromatography, and a white powder was obtained in 93% yield.
Example 8
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=heptadecyl), 0.2mmol of potassium glutamate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction, the target compound IIC (r=heptadecyl) was obtained by separation by column chromatography, and a white powder was obtained in a yield of 90%.
Example 9
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of glutamic acid and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIA (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 93% yield.
Example 10
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of sodium glutamate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIB (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in a yield of 90%.
Example 11
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of potassium glutamate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIC (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 88% yield.
Example 12
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of disodium glutamate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction was completed, the target compound IID (r=undecyl) was obtained by column chromatography separation, and a transparent liquid was obtained in 86% yield.
Example 13
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of glutamic acid TEA salt and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIE (r=undecyl) was obtained by column chromatography separation, and a transparent liquid was obtained in a yield of 85%.
Example 14
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of disodium glutamate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IID (r=9-heptadecenyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in a yield of 87%.
Example 15
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of glutamic acid TEA salt and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIE (r=9-heptadecenyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in a yield of 85%.
Example 16
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of sodium glycinate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound IIIB (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 95%.
Example 17
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of potassium glycinate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIC (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 94%.
Example 18
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of sodium glycinate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIB (r=tridecyl) was obtained by column chromatography separation, and a white powder was obtained in 92% yield.
Example 19
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of potassium glycinate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIC (r=tridecyl) was obtained by column chromatography separation, and a white powder was obtained in 92% yield.
Example 20
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of glycine and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIA (r=7-pentadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in a yield of 90%.
Example 21
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of sodium glycinate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIB (r=7-pentadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 92% yield.
Example 22
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=heptadecyl), 0.2mmol of potassium glycinate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIC (r=heptadecyl) was obtained by separation by column chromatography, and a white powder was obtained in 98% yield.
Example 23
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of sodium glycinate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIB (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 88% yield.
Example 24
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of potassium glycinate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IIIC (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 89% yield.
Example 25
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of sodium alaninate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction, the target compound IVB (r=undecyl) was obtained by column chromatography separation, and a transparent liquid was obtained in a yield of 87%.
Example 26
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of alanine TEA salt and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction, the target compound IVA (r=undecyl) was obtained by column chromatography separation, and a transparent liquid was obtained in a yield of 87%.
Example 27
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of sodium alanine and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound IVB (r=tridecyl) was obtained by column chromatography separation, and a transparent liquid was obtained in a yield of 85%.
Example 28
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of alanine TEA salt and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound IVA (r=tridecyl) was obtained by column chromatography separation, and a transparent liquid was obtained in 89% yield.
Example 29
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of sodium alaninate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IVB (r=7-pentadecenyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in a yield of 87%.
Example 30
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of alanine TEA salt and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IVA (r=7-pentadecenyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in a yield of 84%.
Example 31
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=heptadecyl), 0.2mmol of sodium alaninate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction was completed, the target compound IVB (r=heptadecyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in 83% yield.
Example 32
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=heptadecyl), 0.2mmol of alanine TEA salt and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction was completed, the target compound IVA (r=heptadecyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in 82% yield.
Example 33
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of alanine TEA salt and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound IVB (r=9-heptadecenyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in a yield of 90%.
Example 34
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of sarcosine and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VA (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 91%.
Example 35
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of sarcosine and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VA (r=tridecyl) was obtained by column chromatography separation, and a white powder was obtained in 92% yield.
Example 36
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of sarcosine and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VA (r=7-pentadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 94% yield.
Example 37
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of sarcosine and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VA (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in 92% yield.
Example 38
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=heptadecyl), 0.2mmol of sarcosine and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12h. After the reaction was completed, the target compound VA (r=heptadecyl) was obtained by separation by column chromatography, and a white powder was obtained in 93% yield.
Example 39
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of sarcosine sodium and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VB (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 90%.
Example 40
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of sodium sarcosinate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VB (r=7-pentadecenyl) was obtained by column chromatography separation to obtain a white powder with a yield of 92%.
Example 41
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of potassium sarcosinate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VB (r=undecyl) was obtained by column chromatography separation to obtain a transparent liquid with a yield of 90%.
Example 42
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of sarcosine sodium and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VB (r=tridecyl) was obtained by column chromatography separation, and a transparent liquid was obtained in a yield of 85%.
Example 43
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of sodium sarcosinate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VB (r=9-heptadecenyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in a yield of 85%.
Example 44
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of potassium sarcosinate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VC (r=9-seventeen alkenyl) was obtained by column chromatography separation, and a transparent liquid was obtained in 85% yield.
Example 45
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of sarcosine TEA salt and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction was completed, the target compound VD (r=9-seventeen alkenyl) was obtained by separation by column chromatography, and a transparent liquid was obtained in a yield of 87%.
Example 46
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=undecyl), 0.2mmol of sodium methyltaurine and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIB (r=undecyl) was obtained by column chromatography separation to obtain a white powder with a yield of 80%.
Example 47
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=tridecyl), 0.2mmol of sodium methyltaurate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIB (r=tridecyl) was obtained by column chromatography separation, and white powder was obtained in 82% yield.
Example 48
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=7-pentadecenyl), 0.2mmol of sodium methyltaurate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIB (r=7-pentadecenyl) was obtained by separation by column chromatography, and a white powder was obtained in a yield of 84%.
Example 49
In a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=heptadecyl), 0.2mmol of sodium methyltaurate and 0.1mmol of di-tert-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIB (r=heptadecyl) was obtained by column chromatography separation, and white powder was obtained in a yield of 87%.
Example 50
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of sodium methyltaurate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIB (R=9-seventeen alkenyl) is obtained through column chromatography separation, and white paste is obtained, and the yield is 83%.
Example 51
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of potassium methyltaurate and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIC (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white paste was obtained in a yield of 84%.
Example 52
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of methyltaurine and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIA (r=9-heptadecenyl) was obtained by column chromatography separation, and a white paste was obtained in 89% yield.
Example 53
To a 10mL reaction tube were added 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of methyl taurate and 0.05mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIA (r=9-heptadecenyl) was obtained by column chromatography separation, and a white paste was obtained in 65% yield.
Example 54
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of methyltaurine and 0.1mmol of di-t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 120℃for 12 hours. After the reaction, the target compound VIA (r=9-heptadecenyl) was obtained by separation by column chromatography, and a white paste was obtained in 34% yield.
Example 55
A10 mL reaction tube was charged with 0.2mmol of benzofuranone derivative I (R=9-heptadecenyl), 0.2mmol of methyl taurate and 0.1mmol of t-butyl peroxide, 2mL of toluene, and the reaction was stirred at 140℃for 12 hours. After the reaction, the target compound VIA (r=9-heptadecenyl) was obtained by column chromatography separation, and a white paste was obtained in 80% yield.
Claims (1)
1. A synthesis method of a surfactant containing phenolic hydroxyl amino acid is characterized in that: the benzofuranone compound and amino acid and/or amino acid salt are subjected to oxidative ring opening-condensation tandem reaction under the action of a di-tert-butyl peroxide oxidant to obtain the amino acid surfactant containing phenolic hydroxyl groups;
the benzofuranone compound has a structure shown in formula 1:
1 (1)
Wherein R is C 8 ~C 18 Is a fatty hydrocarbon group of (2);
the amino acid is at least one of glutamic acid, glycine, alanine, sarcosine and methyl taurine;
the amino acid salt is at least one of glutamate, glycinate, alanine salt, sarcosinate and methyl taurate;
the phenolic hydroxyl group-containing amino acid surfactant has a structure shown in a formula 2:
2, 2
Wherein, the liquid crystal display device comprises a liquid crystal display device,
r is C 8 ~C 18 Is a fatty hydrocarbon group of (2);
a is one of the following amino acid groups:、；
m is hydrogen, potassium ion, sodium ion or TEA ion:
the molar amount of the di-tert-butyl peroxide is 25-75% of the molar amount of the benzofuranone compound;
the conditions of the oxidative ring-opening-condensation tandem reaction are as follows: reacting for 8-16 h at the temperature of 120-160 ℃;
the oxidative ring-opening-condensation tandem reaction adopts at least one of acetonitrile, toluene and chlorobenzene as a solvent.
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| CN101842361A (en) * | 2007-06-27 | 2010-09-22 | 阿斯利康(瑞典)有限公司 | Pyrazinone derivatives and their use in the treatment of lung diseases |
| CN109534975A (en) * | 2019-01-04 | 2019-03-29 | 湖南大学 | A kind of efficient catalytic synthetic method of 2- hydroxy benzophenone ketone compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101842361A (en) * | 2007-06-27 | 2010-09-22 | 阿斯利康(瑞典)有限公司 | Pyrazinone derivatives and their use in the treatment of lung diseases |
| CN109534975A (en) * | 2019-01-04 | 2019-03-29 | 湖南大学 | A kind of efficient catalytic synthetic method of 2- hydroxy benzophenone ketone compound |
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| Title |
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| Synthesis, Application and Kinetic Studies of Chiral Phosphite- Oxazoline Palladium Complexes as Active and Selective Catalysts in Intermolecular Heck Reactions;Zahra Mazloomi等;Adv. Synth. Catal;第360卷;1650-1664 * |
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