CN119552087A - A kind of synthetic method of dialkylamino alcohol - Google Patents
A kind of synthetic method of dialkylamino alcohol Download PDFInfo
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- CN119552087A CN119552087A CN202411753892.2A CN202411753892A CN119552087A CN 119552087 A CN119552087 A CN 119552087A CN 202411753892 A CN202411753892 A CN 202411753892A CN 119552087 A CN119552087 A CN 119552087A
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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Abstract
The invention discloses a synthesis method of dialkylamino alcohol, which is obtained by reacting dialkylamino ester with a Grignard reagent. The synthetic route provided by the invention has mild overall synthesis conditions, readily available raw materials and low toxicity.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of dialkyl amino alcohol.
Background
Dialkylamino alcohol compounds are important organic intermediates useful in the synthesis of a variety of drug substances, and can also be used in the synthesis of metal amino alkoxide complexes, a common precursor useful for the deposition of related metals and their compounds, such as a precursor containing dimethylamino-2-propoxy (dmamp) or dimethylamino-2-butoxy (dmamb) ligands.
The most common synthetic method for the synthesis of dialkylaminoalcohols is by heating and refluxing epoxide and dialkylamine in an autoclave, and reference is made to patent US3954873 (1976). The main disadvantages of this method are that the reaction temperature is too high and high pressure is required, benzene solvent is used for filtration in the post-treatment, and benzene has high toxicity.
Disclosure of Invention
The invention aims to provide a novel synthesis method of dialkylamino alcohol, wherein the dialkylamino alcohol has the following general formula (I),
The synthesis method comprises the steps of a, reacting dialkyl amino ester shown in a general formula (II) with a Grignard reagent shown in a general formula (III);
wherein R 1-R5 independently represents lower alkyl, and X 1 is halogen.
Preferably, in the case that R 3 and R 4 are different, the method further comprises a step b of adding a quenching agent into the reaction liquid in the step a, separating to obtain dialkyl amino ketone shown in the general formula (IV) after quenching, and reacting the dialkyl amino ketone with a Grignard reagent shown in the general formula (V) to prepare dialkyl amino alcohol shown in the general formula (I);
Wherein X 2 is halogen.
Preferably, step c is further comprised, prior to step a, of obtaining a dialkylaminoester of general formula (II) by reacting a dialkylamine with a haloacetate, the reaction formula being represented as follows:
Step a specifically comprises dissolving a dialkylamino ester in a solvent A, and adding a Grignard reagent into the reaction system under a low temperature condition. The solvent a is preferably tetrahydrofuran.
Step B specifically comprises dissolving dialkylaminoketone in solvent B, adding Grignard reagent into the reaction system under low temperature condition, and continuously reacting under low temperature condition. The solvent B is preferably an ether solvent, and can be selected from one of THF, diethyl ether, 1, 4-dioxane and methyl tertiary butyl ether. This step can also be referred to in reference TetrahedronLetters No.41, pp 3625-3628,1977.
The step C specifically comprises dissolving dialkylamine in solvent C at low temperature, adding haloacetate into the reaction system, and rectifying and separating to obtain dialkylaminoester after the reaction. The reaction temperature is-20-0 ℃. The solvent C is selected from one of ethyl acetate, toluene, butyl acetate, methyl acetate and isopropyl acetate. The molar ratio of the halogenated acetate to the dialkylamine is 1 (2-3). The reaction time is 12-24 h. This step can also be referred to patent CN113620825A.
Preferably, R 1 and R 2 are both methyl.
Preferably, R 3 is methyl or ethyl and R 4 is methyl.
The invention provides a new synthesis route of dialkylamino alcohol, which adopts dialkylamino ester to react with Grignard reagent, and has mild overall synthesis condition, easily obtained raw materials and low toxicity.
Detailed Description
The following examples are provided to illustrate the above features and advantages of the present invention. The method of the invention is a conventional method in the art unless specifically stated otherwise.
[ Example 1]
The synthesis of 1-dimethylamino-2-methyl-2-butanol in this example specifically comprises the steps of:
(1) Dissolving dimethylamine in toluene cooled to-20-0 ℃, dropwise adding ethyl chloroacetate, controlling the molar ratio of the ethyl chloroacetate to the dimethylamine to be 1 (2-3), stirring for 12-24 hours, filtering out formed precipitate, distilling off solvent toluene, and rectifying in vacuum to obtain the product. The ethyl chloroacetate is easy to obtain and stable at normal temperature. Dimethylamine is gas, and the introducing time of dimethylamine is determined by weighing according to the aeration size and the cooling temperature.
(2) N, N-dimethylaminoalcohol is prepared by reacting N, N-dimethylaminoethyl acetate with methyl and ethyl Grignard reagents in two steps to obtain 1-dimethylamino-2-methyl-2-butanol. And (3) dropwise adding the Grignard reagent into the ethyl dimethylaminoacetate at a low temperature, and continuing stirring for reaction. The reaction is simple, the condition is mild, and the Grignard reagent is easy to obtain.
The reaction equation for 1-dimethylamino-2-methyl-2-butanol is shown below:
Wherein, the N, N-dimethylamino ethyl acetate is respectively reacted with methyl and ethyl Grignard reagent in two steps to synthesize, specifically:
And (2-1) adding N, N-dimethylamino ethyl acetate and tetrahydrofuran solvent into a reaction kettle, cooling to-20-0 ℃, slowly dropwise adding ethyl magnesium bromide, controlling the molar ratio of the N, N-dimethylamino ethyl acetate to the ethyl magnesium bromide to be 1 (1-1.2), continuing to perform heat preservation and stirring reaction for 1-3 hours after the dropwise adding, adding acetic acid solution to quench a reaction system, extracting the reaction liquid by diethyl ether, and distilling to obtain the 1- (dimethylamino) -2-butanone. Wherein the concentration of the acetic acid solution was 10.4wt%, and the addition amount of acetic acid was 1.5 equivalents of ethyl magnesium bromide.
(2-2) Adding 1- (dimethylamino) -2-butanone and solvent diethyl ether into a reaction kettle, cooling to-10-0 ℃, slowly dropwise adding methyl magnesium bromide, controlling the molar ratio of 1- (dimethylamino) -2-butanone to methyl magnesium bromide to be 1 (1-1.5), stirring the mixture at room temperature for 2-4 day, quenching the mixture through saturated ammonium chloride solution after reaction, extracting the mixture through ethyl acetate, and distilling the mixture to obtain 1- (dimethylamino) -2-methyl-2-butanol.
The prepared 1-dimethylamino-2-methyl-2-butanol can be used for preparing metal complexes of corresponding alkylamino alcohols, such as nickel alkylamino alcohols, specifically comprising the steps of:
Adding sodium hydride with the purity of 99% and tetrahydrofuran serving as a solvent into a reaction kettle, cooling to-30-0 ℃, slowly adding tetrahydrofuran solution of amino alcohol dropwise, continuously stirring for 2-8 hours at room temperature after the dropwise addition is finished, filtering, and vacuum drying to obtain sodium salt of the amino alcohol;
Adding [ Ni (NH 3)6]Cl2 and toluene into a reaction kettle, slowly adding sodium salt of amino alcohol, [ Ni (NH 3)6]Cl2 and sodium salt of amino alcohol) with a molar ratio of 1 (2-2.5), stirring for 8h under reflux, cooling, filtering the reaction mixture, removing volatile matters under vacuum to obtain a crude product, and sublimating to obtain a pure product.
[ Example 2]
The synthesis of 1-dimethylamino-2-methyl-2-propanol in this example specifically comprises the steps of:
(1) Dissolving dimethylamine in toluene cooled to-20-0 ℃, dropwise adding ethyl chloroacetate, controlling the molar ratio of the ethyl chloroacetate to the dimethylamine to be 1 (2-3), stirring for 12-24 hours, filtering out formed precipitate, distilling off solvent toluene, and rectifying in vacuum to obtain the product. The ethyl chloroacetate is easy to obtain and stable at normal temperature.
(2) And (3) preparing N, N-dimethyl amino alcohol, namely adding N, N-dimethyl amino ethyl acetate and tetrahydrofuran serving as a solvent into a reaction kettle, cooling to-78-0 ℃, slowly dropwise adding methyl magnesium bromide, controlling the molar ratio of the N, N-dimethyl amino ethyl acetate to the methyl magnesium bromide to be 1 (2-10), slowly heating to room temperature after the dropwise addition is finished, stirring for reacting for 1-48 hours, adding saturated ammonium chloride solution to quench a reaction system, extracting reaction liquid by diethyl ether, and distilling to obtain the 1-dimethylamino-2-methyl-2-propanol.
The reaction equation for 1-dimethylamino-2-methyl-2-propanol is shown below:
[ example 3]
The synthesis of N, N-dimethylamino-2-methyl-2-butanol in this example specifically comprises the steps of:
Step one, preparing N, N-dimethylamino ethyl acetate
9G of dimethylamine (0.20 mol) was introduced into 200mL of toluene as a solvent at 0℃and 12.2g of ethyl chloroacetate (0.10 mol) was added dropwise thereto, followed by stirring for 24 hours at the temperature, the precipitate was removed by filtration, toluene was removed by distillation, and 10.49g of N, N-dimethylaminoethyl acetate was obtained by vacuum distillation (10 Torr) at a distillation temperature of 55-58℃and a yield of 80%.
Step two, preparing N, N-dimethylamino-2-butanone
10.49G of ethyl N, N-dimethylaminoacetate (0.08 mol) obtained in the first step is dissolved in 100mL of tetrahydrofuran in an inert gas atmosphere, the temperature is reduced to-15 ℃, 40mL of ethyl magnesium bromide tetrahydrofuran solution (2M) is slowly added, after the dropwise addition is finished, the mixture is kept warm and stirred for 3 hours, 10.4% of acetic acid solution is added, stirring is continued for 0.5 hour, the reaction solution is extracted for 3 times by using diethyl ether, and 6.54g of 1- (dimethylamino) -2-butanone is obtained by distillation, and the product is 71%.
Step three, preparing N, N-dimethylamino-2-methyl-2-butanol
6.54G of 1- (dimethylamino) -2-butanone (56.8 mmol) obtained in step two was dissolved in 60mL of diethyl ether under an inert atmosphere, the temperature was lowered to-10℃and 28.5mL of diethyl ether solution of methyl magnesium bromide (2M) was added dropwise, slowly warmed to room temperature and stirred for 3day, the saturated ammonium chloride solution was quenched, extracted with ethyl acetate, and 4.8g of 1- (dimethylamino) -2-methyl-2-butanol was obtained by distillation in 65% yield.
The prepared N, N-dimethylamino-2-methyl-2-butanol can be used for preparing corresponding metal complexes, and the specific steps are as follows:
Step four, preparing N, N-dimethylamino-2-methyl-2-butanol sodium salt
0.63G of sodium hydride (26 mmol, purity 99%) and 50mL of tetrahydrofuran are added into a three-necked flask, the temperature is reduced to-10 ℃, the tetrahydrofuran solution (26 mmol, 2M) of the amino alcohol obtained in the step three is slowly added dropwise, after the dropwise addition, the mixture is cooled to room temperature, stirring is continued for 6h, filtration and vacuum drying are carried out, and 3.6g of sodium salt of the amino alcohol is obtained, and the yield is 91%.
Preparing a dimethyl amino alcohol nickel complex
2.28G of [ Ni (NH 3)6]Cl2 (12 mmol) ] was dissolved in 30mL of toluene under inert atmosphere, the sodium salt of aminoalcohol (24 mmol) obtained in step four was slowly added, stirred under reflux for 8h, after cooling, the reaction mixture was filtered, and the volatiles were removed under vacuum to give crude product, followed by sublimation to give 2.64g of pure product.
[ Example 4]
The synthesis of N, N-dimethylamino-2-methyl-2-propanol in this example specifically comprises the steps of:
Step one, preparing N, N-dimethylamino ethyl acetate
9G of dimethylamine (0.20 mol) was introduced into 200mL of toluene as a solvent at 0℃and 12.2g of ethyl chloroacetate (0.10 mol) was added dropwise thereto, followed by stirring for 24 hours at the temperature, and then the precipitate was removed by filtration, toluene was removed by distillation, and N, N-dimethylaminoethyl acetate (10.49 g; 10 Torr) was obtained by vacuum distillation at 55-58℃in 80% yield.
Step two, preparing N, N-dimethylamino-2-methyl-2-propanol
10.49G of ethyl N, N-dimethylaminoacetate (0.08 mol) obtained in the step one was dissolved in 60mL of tetrahydrofuran under an inert atmosphere, the temperature was lowered to-40℃and 80mL of a solution of methylmagnesium bromide in tetrahydrofuran (2M) was added dropwise, the mixture was slowly warmed to room temperature and stirred for 2day, the saturated ammonium chloride solution was quenched, extracted with diethyl ether, and 7.9g of 1- (dimethylamino) -2-methyl-2-propanol was obtained by distillation in 85% yield.
Examples 5 to 6
The conditions were the same as in example 3, and the addition amount of dimethylamine in step one was increased, and the specific results were shown in the following table:
| Examples | Dimethylamine | Yield is good |
| Example 3 | 9g(0.2mol) | 80% |
| Example 5 | 11.3g(0.25mol) | 85% |
| Example 6 | 13.6g(0.30mol) | 87% |
Examples 7 to 9
The conditions were the same as in example 3, and the reaction solvent in the second step was replaced with diethyl ether, 1, 4-dioxane and methyl t-butyl ether, and the specific results were shown in the following table:
| Examples | Solvent(s) | Yield is good |
| Example 3 | Tetrahydrofuran (THF) | 71% |
| Example 7 | Diethyl ether | 70% |
| Example 8 | 1, 4-Dioxahexacyclic ring | 65% |
| Example 9 | Methyl tert-butyl ether | 68% |
Examples 10 to 12
The conditions were the same as in example 3, and the amount of ethyl magnesium bromide added in step II was controlled to 50 to 70mL, and the data for obtaining 1- (dimethylamino) -2-butanone were as follows:
| Examples | Ethyl magnesium bromide addition (mL) | Yield is good |
| Example 3 | 40 | 71% |
| Example 10 | 50 | 75% |
| Example 11 | 60 | 68% |
| Example 12 | 70 | 55% |
Examples 13 to 15
The conditions were the same as in example 4, and the amount of methyl magnesium bromide added in step two was controlled to 80 to 140mL, and the data for obtaining 1- (dimethylamino) -2-methyl-2-propanol were as follows:
[ example 16 ]
The conditions were the same as in example 3, and the stirring time at room temperature in step three was controlled at 1day to give 4.1g of 1- (dimethylamino) -2-methyl-2-butanol in a calculated yield of 55%.
[ Example 17 ]
The conditions were the same as in example 3, and the stirring time at room temperature in the fourth step was controlled to 2 hours, whereby 3.16g of the sodium salt of aminoalcohol was obtained, and the calculated yield was 80%.
Example 18
The conditions were the same as in example 3, and the amount of the sodium salt of the aminoalcohol added in the fifth step was controlled to 3.9g (26 mmol), whereby a nickel dimethylaminoalcohol complex having a mass of 2.8g was obtained, and the calculated yield was 70%.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A method for synthesizing a dialkylamino alcohol, wherein the dialkylamino alcohol has a structure of the following general formula (I):
;
The synthesis method comprises the steps of a, reacting dialkyl amino ester shown in a general formula (II) with a Grignard reagent shown in a general formula (III);
,
R3MgX1 (III),
wherein R 1-R5 independently represents lower alkyl, and X 1 is halogen.
2. The method according to claim 1, wherein in the case that R 3 and R 4 are different, the method further comprises the step b of adding a quenching agent into the reaction liquid in the step a, separating the quenching agent to obtain the dialkylaminoketone shown in the general formula (IV), and reacting the dialkylaminoketone with the Grignard reagent shown in the general formula (V) to prepare the dialkylaminoalcohol shown in the general formula (I);
,
R4MgX2 (V),
Wherein X 2 is halogen.
3. The process according to claim 1, wherein step a comprises dissolving a dialkylamino ester in solvent a, and adding a grignard reagent to the reaction system at low temperature.
4. A process according to claim 3, wherein solvent a is an ethereal solvent.
5. The method according to claim 2, wherein step B comprises dissolving the dialkylaminoketone in solvent B, adding the grignard reagent to the reaction system at low temperature, and continuing the reaction at low temperature.
6. The method according to claim 5, wherein the solvent B is one of THF, diethyl ether, 1, 4-dioxane and methyl tert-butyl ether.
7. The process according to claim 1, wherein the dialkylaminoester of formula (II) is obtained by reacting a dialkylamine with a haloacetate, the reaction formula being represented by:
。
8. The method according to claim 7, wherein the preparation of the dialkylamino ester comprises dissolving the dialkylamino ester in the solvent C at low temperature, adding the haloacetate into the reaction system, and rectifying and separating to obtain the dialkylamino ester after the reaction.
9. The method of claim 8, wherein in the preparation process of the dialkylamino ester, the reaction temperature is in a range of-20-0 ℃, the solvent C is one of ethyl acetate, toluene, butyl acetate, methyl acetate and isopropyl acetate, the molar ratio of the halogenated acetate to the dialkylamine is in a range of 1 (2-3), and the reaction time is 12-24 hours.
10. The method of claim 1, wherein R 1 and R 2 are each methyl, R 3 is methyl or ethyl, and R 4 is methyl.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02282350A (en) * | 1989-04-24 | 1990-11-19 | Nitto Denko Corp | Production of n,n-dimethyl-3-amino-2-propanol |
| CN112105385A (en) * | 2017-12-26 | 2020-12-18 | 凯麦拉医疗公司 | IRAK degrading agents and uses thereof |
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- 2024-12-02 CN CN202411753892.2A patent/CN119552087A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02282350A (en) * | 1989-04-24 | 1990-11-19 | Nitto Denko Corp | Production of n,n-dimethyl-3-amino-2-propanol |
| CN112105385A (en) * | 2017-12-26 | 2020-12-18 | 凯麦拉医疗公司 | IRAK degrading agents and uses thereof |
Non-Patent Citations (4)
| Title |
|---|
| D. V. TRUKHIN等: "New Spin Probes: Tri- and Hexacationic Derivatives of Stable Tetrathiatriarylmethyl Radicals", 《RUSSIAN JOURNAL OF ORGANIC CHEMISTRY》, vol. 55, no. 3, 31 December 2019 (2019-12-31), pages 296, XP036777053, DOI: 10.1134/S1070428019030035 * |
| M. VISCONTINI UND J. MEIER.: "227. N-Dimethylglycin-hydrazid-hydrochlorid, Reagenz zur Isolierung und Charakterisierung von Carbonyl-Derivate", 《VOLUMEN XXXIII, FASCICULUS VI》, vol. 227, 31 December 1950 (1950-12-31), pages 1773 - 1775 * |
| RENÉ PETERS等: "Practical formal total synthesis of (rac)- and (S)-camptothecin", 《ORG. BIOMOL. CHEM.》, vol. 4, 22 December 2005 (2005-12-22), pages 498 - 509, XP002378337, DOI: 10.1039/b514147h * |
| WILLIAM I. NICHOLSON等: "Direct Amidation of Esters by Ball Milling", 《ANGEW. CHEM. INT. ED.》, vol. 60, 31 August 2021 (2021-08-31), pages 21868 * |
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