CN110003057B - Preparation method of sulfonylguanidine compound - Google Patents
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
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Abstract
The invention relates to a preparation method of a sulfonyl guanidine compound, and mainly provides a novel method for constructing the sulfonyl guanidine compound by inserting two molecules of amine through the reaction of sulfonyl azide participated by 4, 5-dimethyl aryl diisonitrile and amine under the catalysis of cobalt.
Description
Technical Field
The invention belongs to the field of chemical medicines, and relates to a preparation method of a sulfonylguanidine compound.
Background
The guanidyl functional group has the characteristics of easy formation of hydrogen bonds, high stability, strong biological and pharmacological activity and the like, and thus has received wide attention from chemists and pharmacologists. Guanidino compounds are used in a wide variety of molecular recognition, pharmacological activity, catalysis, coordination, and synthesis. For example, ZANAMIVIR (ZANAMIVIR) is a drug against influenza virus; important structural units in common antihypertensive drugs guanethidine (Guanethdine), antihyperglycemic drugs Phenformin hydrochloride (Phenformin hydrochloride) and antiviral drugs aclacinavir (Acyclovir) are all guanidyl functional groups; in addition, studies have shown that Crambine A, Crambine B and Ptilomycin A have potential anti-AIDS activity and Eusyntylamide has anti-cancer activity. Among them, sulfonylguanidines are important structural units in many drugs (e.g., sulfaguanidine).
Various methods for synthesizing sulfonylguanidine compounds have been reported. Tomislav subject group for the first time in 2014The work of constructing the sulfonylguanidine compound by a sulfonamide and carbodiimide one-pot method is reported, the reaction needs to be carried out under the nitromethane condition with certain danger, and the substrate universality of the reaction is not high. The Zhang-Hua topic group of China agricultural university in 2017 made a new effort in the synthesis of sulfonyl guanidine compounds, and the new effort successfully constructs the sulfonyl guanidine compounds by using sulfonyl azide, isonitrile and phenylboronic acid through a two-step pot method under the catalysis of rhodium. However, the working has the disadvantages of expensive catalyst, long reaction time, high temperature and the like. Then the subject group reacts sulfonyl azide, isonitrile and secondary amine under palladium catalysis in a one-pot method to synthesize the sulfonyl guanidine compound. The method has short reaction time, can be finished within 2 hours, but has the defects of relatively high cost of the catalyst and need of adding ligand (dppp) or alkali (K)2CO3) And the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a novel preparation method of a sulfonyl guanidine compound.
The invention provides a preparation method of a compound shown as a formula IV on one hand, which comprises the step of reacting a compound shown as a formula I, a compound shown as a formula II and a compound shown as a formula III in the presence of a cobalt catalyst,
wherein R is1Selected from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl;
R2selected from the group consisting of alkyl, alkenyl, alkynyl, carboxyl, carboxylate, cycloalkyl, heterocyclyl, aryl and heteroaryl, wherein said alkyl, alkenyl, alkynyl, carboxyl, carboxylate, cycloalkyl, heterocyclyl, aryl and heteroaryl are optionally substituted with one or more substituents selected from the group consisting of alkyl, halogen, hydroxyl, amino, oxy, carboxyl, nitro, cyano, alkoxy, cycloalkyl, heterocyclyl, aryl and heteroaryl;
R3selected from alkyl and alkenylAlkynyl, halogen, hydroxy, amino, oxy, carboxy, nitro, cyano, alkoxy, cycloalkyl, heterocyclyl, aryl and heteroaryl, wherein said hydroxy, amino, carboxy are optionally protected by a protecting group, wherein said alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl are optionally substituted by one or more substituents selected from the group consisting of alkyl, halogen, hydroxy, amino, oxy, carboxy, nitro, cyano and alkoxy,
n is selected from 0, 1,2 and 3.
Cobalt catalysts include, but are not limited to, CoC2O4、CoCl2、Co(acac)2、CoBr2、Co2(CO)8Preferably Co (acac)2。
In certain embodiments, R1Selected from alkyl, phenyl, naphthyl, thienyl, pyridyl, preferably phenyl.
In certain embodiments, R2Selected from benzyl, carboxylate, aryl, wherein said aryl is optionally substituted by one or more substituents selected from halogen, hydroxy, amino, oxy, carboxy, alkyl, nitro, cyano, alkoxy, preferably R2Is phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl and benzyl.
In certain embodiments, R3Selected from the group consisting of alkyl, halogen, hydroxy, amino, oxy, carboxy, nitro, cyano and alkoxy, wherein said hydroxy, amino, carboxy are optionally protected by a protecting group, and wherein said alkyl is optionally substituted with one or more substituents selected from the group consisting of halogen, hydroxy, amino, oxy, carboxy, nitro, cyano and alkoxy.
In certain embodiments, the compound of formula I is
The molar ratio of the compound shown in the formula I to the compound shown in the formula II can be 1: 1-1: 10, and preferably 1: 1-1: 5.
The molar ratio of the compound shown in the formula I to the compound shown in the formula III can be 1: 1-1: 10, and preferably 1: 1-1: 5.
The molar ratio of the compound shown in the formula I to the metal salt catalyst can be 1: 0.01-1: 10, and preferably 1: 0.05-1: 1.
In certain embodiments, the molar ratio of the compound of formula I, the compound of formula II, and the compound of formula III is 1:2.2: 2.
The solvent for the reaction may be a conventional solvent, and for example, may be one or more of dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1-methyl-2-pyrrolidone, tetrahydrofuran, methyltetrahydrofuran, dioxane, toluene, xylene, dimethylsulfoxide, diethyl ether, isopropyl ether, methyl t-butyl ether, acetonitrile, propionitrile, isopropanol, propanol, ethanol, methanol, dichloromethane, dichloroethane, chloroform, preferably dimethylacetamide, acetonitrile, dimethylsulfoxide, dichloroethane, more preferably acetonitrile.
In certain embodiments, the reaction is carried out in the presence of water. The volume ratio of water to solvent may be from 1:10 to 1:50, preferably 1: 20.
The reaction temperature may be from 0 ℃ to 200 ℃, preferably from 10 ℃ to 100 ℃, more preferably 80 ℃.
The reaction time may be more than 1 hour, preferably 6 hours.
In certain embodiments, the reaction solvent is acetonitrile, the reaction contains water, the volume ratio of water to acetonitrile is 1:20, the reaction temperature is 80 ℃, and the reaction time is 6 hours.
In another aspect, the invention provides a method for preparing sulfadiazine, which comprises the preparation method of the compound shown in the formula IV.
In certain embodiments, R1Is p-aminophenyl.
In certain embodiments, R2Is phenyl, p-methylphenyl, p-methoxybenzeneP-fluorophenyl and benzyl.
In certain embodiments, the method further comprises the step of converting the compound of formula IV to sulfadiazine.
The invention provides a novel method for constructing a sulfonylguanidine compound by inserting two molecules of amine into the reaction of sulfonyl azide participated by 4, 5-dimethyl aryl diisonitrile and the amine under the catalysis of cobalt, and the method has good yield, can be used for preparing medicines such as sulphaguanidine and the like, and is suitable for industrial production.
Unless stated to the contrary, terms used in the specification and claims have the following meanings.
The term "alkyl" refers to a saturated aliphatic hydrocarbon group which is a straight or branched chain group containing 1 to 20 carbon atoms, preferably an alkyl group containing 1 to 12 carbon atoms. Non-limiting examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1, 2-trimethylpropyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2, 3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2, 3-dimethylpentyl, 2, 4-dimethylpentyl, 2-dimethylpentyl, 3-dimethylpentyl, 2-ethylpentyl, 3-ethylpentyl, n-octyl, 2, 3-dimethylhexyl, 2, 4-dimethylhexyl, 2, 5-dimethylhexyl, 2-dimethylhexyl, 3-dimethylhexyl, 4-dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methyl-2-ethylpentyl, 2-methyl-3-ethylpentyl, n-nonyl, 2-methyl-2-ethylhexyl, 2-methyl-3-ethylhexyl, 2-dimethylpentyl, 2-dimethylhexyl, 3-dimethylpentyl, 2-ethylhexyl, 3-dimethylhexyl, 2-ethylhexyl, 2-dimethylhexyl, 2-ethylhexyl, 2-dimethylhexyl, 2-dimethylhexyl, 2-dimethylhexyl, 2-ethylhexyl, 2-ethyl, 2-2, 2-2, 2-2, or, 2, 2-diethylpentyl, n-decyl, 3-diethylhexyl, 2-diethylhexyl, and various branched isomers thereof. More preferred are lower alkyl groups having 1 to 6 carbon atoms, non-limiting examples of which include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1, 2-trimethylpropyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2, 3-dimethylbutyl and the like. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent may be substituted at any available point of attachment, preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halo, mercapto, hydroxy, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkoxy, heterocycloalkoxy, cycloalkylthio, heterocycloalkylthio, oxo, carboxy or carboxylate.
The term "cycloalkyl" refers to a saturated or partially unsaturated monocyclic or polycyclic cyclic hydrocarbon substituent, the cycloalkyl ring containing from 3 to 20 carbon atoms, preferably from 3 to 12 carbon atoms, more preferably from 3 to 6 carbon atoms. Non-limiting examples of monocyclic cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptatrienyl, cyclooctyl, and the like; polycyclic cycloalkyl groups include spiro, fused and bridged cycloalkyl groups.
The term "heterocyclyl" refers to a saturated or partially unsaturated mono-or polycyclic cyclic hydrocarbon substituent containing from 3 to 20 ring atoms wherein one or more of the ring atoms is selected from nitrogen, oxygen, or S (O)m(wherein m is an integer from 0 to 2) but excludes the ring moiety of-O-O-, -O-S-, or-S-S-, the remaining ring atoms being carbon. Preferably 3 to 12 ring atoms, of which 1 to 4 are heteroatoms; more preferably from 3 to 6 ring atoms. Non-limiting examples of monocyclic heterocyclyl groups include pyrrolidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, dihydroimidazolyl, dihydrofuranyl, dihydropyrazolyl, dihydropyrrolyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, homopiperazinyl, and the like, with piperidinyl, pyrrolidinyl being preferred. Polycyclic heterocyclic groups include spiro, fused and bridged heterocyclesA cyclic group.
The term "aryl" refers to a 6 to 14 membered all carbon monocyclic or fused polycyclic (i.e., rings which share adjacent pairs of carbon atoms) group having a conjugated pi-electron system, preferably 6 to 10 membered, such as phenyl and naphthyl.
The aryl group may be substituted or unsubstituted, and when substituted, the substituent is preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halogen, mercapto, hydroxy, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkoxy, heterocycloalkoxy, cycloalkylthio, heterocycloalkylthio, carboxy or carboxylate, preferably phenyl.
The term "heteroaryl" refers to a heteroaromatic system comprising 1 to 4 heteroatoms, 5 to 14 ring atoms, wherein the heteroatoms are selected from oxygen, sulfur and nitrogen. Heteroaryl is preferably 5 to 12 membered, such as imidazolyl, furyl, thienyl, thiazolyl, pyrazolyl, oxazolyl, pyrrolyl, tetrazolyl, pyridyl, pyrimidinyl, thiadiazole, pyrazinyl and the like, preferably imidazolyl, pyrazolyl, pyrimidinyl or thiazolyl; more preferably pyrazolyl or thiazolyl.
Heteroaryl groups may be optionally substituted or unsubstituted, and when substituted, the substituents are preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halogen, mercapto, hydroxyl, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkoxy, heterocycloalkoxy, cycloalkylthio, heterocycloalkylthio, carboxyl or carboxylate groups.
The term "alkenyl" refers to a straight or branched chain group having 2 to 20 carbons, preferably 2 to 12 carbons and more preferably 2 to 8 carbons in the main chain, which includes one or more double bonds in the main chain, such as vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 4-dodecenyl, 4,8, 12-tetradecatriene, and the like. "substituted alkenyl" includes alkenyl optionally substituted with one or more substituents, including, for example, those substituents set forth in the definitions of "substituted alkyl" and "substituted cycloalkyl" above.
The term "alkynyl" refers to a straight or branched chain group having 2 to 20 carbons, preferably 2 to 12 carbons, and more preferably 2 to 8 carbons in the backbone, which includes one or more triple bonds in the backbone, such as 2-propynyl, 3-butynyl, 2-butynyl, 4-pentynyl, 3-pentynyl, 2-hexynyl, 3-hexynyl, 2-heptynyl, 3-heptynyl, 4-heptynyl, 3-octynyl, 3-nonynyl, 4-decynyl, 3- ^ alkynyl, 4-dodecynyl, and the like. "substituted alkynyl" includes alkynyl groups optionally substituted with one or more substituents, including, for example, substituents described above in the definition of "substituted alkyl" and "substituted cycloalkyl".
The term "alkoxy" refers to-O- (alkyl) and-O- (unsubstituted cycloalkyl), wherein alkyl is as defined above. Non-limiting examples of alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy. Alkoxy groups may be optionally substituted or unsubstituted, and when substituted, the substituents are preferably one or more groups independently selected from alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, halogen, mercapto, hydroxy, nitro, cyano, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, cycloalkoxy, heterocycloalkoxy, cycloalkylthio, heterocycloalkylthio, carboxy or carboxylate groups.
The term "hydroxyalkyl" refers to an alkyl group substituted with a hydroxy group, wherein alkyl is as defined above.
The term "haloalkyl" refers to an alkyl group substituted with a halogen, wherein alkyl is as defined above.
The term "deuterated alkyl" refers to an alkyl group substituted with a deuterium atom, wherein alkyl is as defined above.
The term "hydroxy" refers to an-OH group.
The term "halogen" refers to fluorine, chlorine, bromine or iodine.
The term "amino" refers to the group-NH2。
The term "cyano" refers to — CN.
The term "nitro" means-NO2。
The term "carboxy" refers to-C (O) OH.
The term "aldehyde" refers to — CHO.
The term "carboxylate" refers to-C (O) O (alkyl) or-C (O) O (cycloalkyl), wherein alkyl, cycloalkyl are as defined above.
The term "acyl halide" refers to a compound containing a group that is-C (O) -halogen.
"optional" or "optionally" means that the subsequently described event or circumstance may, but need not, occur, and that the description includes instances where the event or circumstance occurs or does not. For example, "a heterocyclic group optionally substituted with an alkyl" means that an alkyl may, but need not, be present, and the description includes the case where the heterocyclic group is substituted with an alkyl and the heterocyclic group is not substituted with an alkyl.
"substituted" means that one or more, preferably up to 5, more preferably 1 to 3, hydrogen atoms in the group are independently substituted with a corresponding number of substituents. It goes without saying that the substituents are only in their possible chemical positions, and that the person skilled in the art is able to determine (experimentally or theoretically) possible or impossible substitutions without undue effort. For example, amino or hydroxyl groups having free hydrogen may be unstable in combination with carbon atoms having unsaturated (e.g., olefinic) bonds.
The hydroxyl-protecting Groups of the invention are suitable Groups known in the art for hydroxyl protection, see the literature ("Protective Groups in Organic Synthesis", 5)Th Ed.T.W.Greene&P.g.m.wuts). By way of example, the hydroxyl protecting group may preferably be (C)1-10Alkyl or aryl)3Silane groups, for example: triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl and the like; may be C1-10Alkyl or substituted alkyl, preferably alkoxy or aryl substituted alkyl, more preferably C1-6Alkoxy-substituted C1-6Alkyl or phenyl substituted C1-6Alkyl, most preferably C1-4Alkoxy-substituted C1-4Alkyl groups, for example: methyl, t-butyl, allyl, benzyl, methoxymethyl (MOM), ethoxyethyl, 2-Tetrahydropyranyl (THP), and the like; may be (C)1-10Alkyl or aryl) acyl groups, such as: formyl, acetyl, benzoyl and the like; may be (C)1-6Alkyl or C6-10Aryl) sulfonyl; or (C)1-6Alkoxy or C6-10Aryloxy) carbonyl.
"carboxyl protecting Groups" are suitable Groups known in the art for carboxyl protection, see the literature ("Protective Groups in Organic Synthesis", 5)Th Ed.T.W.Greene&P.g.m.wuts), the carboxyl protecting group may be, for example, preferably a substituted or unsubstituted C1-10Straight or branched alkyl, substituted or unsubstituted C2-10Straight or branched alkenyl or alkynyl, substituted or unsubstituted C3-8With a cyclic alkyl group, substituted or unsubstituted C5-10Aryl or heteroaryl of (A), (B), (C) or (C)1-8Alkyl or aryl)3A silane group; preferably C1-6Straight or branched alkyl of (2), more preferably C1-4Linear or branched alkyl. For example, methyl, ethyl, allyl, isopentenyl, trimethylsilylethyl, and the like.
"amino-protecting Groups" are suitable Groups for amino protection known in the art, see the literature ("Protective Groups in Organic Synthesis", 5)Th.Ed.T.W.Greene&M.wuts), preferably, the amino protecting group may be (C)1-10Alkyl or aryl) acyl groups, such as: formyl, acetyl, benzoyl and the like; may be (C)1-6Alkyl or C6-10Aryl) sulfonyl; or (C)1-6Alkoxy or C6-10Aryloxy) carbonyl, Boc or Cbz; it may also be an alkyl group, for example: trityl (Tr), 2, 4-Dimethoxybenzyl (DMB), p-methoxybenzyl (PMB) or benzyl (Bn).
Detailed Description
The present invention will be explained in detail with reference to specific examples below, so that those skilled in the art can more fully understand the specific examples of the present invention to illustrate the technical solutions of the present invention, and not to limit the present invention in any way.
Example 1
To a common reaction tube were added 1a (39.4mg, 0.2mmol), 2a (41mg, 0.44mmol), 3a (62.5mg, 0.4mmol), Co (acac)2(5 mol%) and CH3CN/H2O (2 mL/100. mu.L), and the reaction was stirred at 80 ℃ for 6 h. After the reaction, silica gel powder was added, the organic solvent was removed by rotary evaporation under reduced pressure, and the product was purified by silica gel column chromatography (ethyl acetate/petroleum ether: 1 to 1:10) to obtain the desired product in an amount of 56.3mg in total of 4aaa in a yield of 77%.
Example 2
Preparation of 4aaa was carried out according to the method and reactants of example 1 using the catalysts, solvents, reaction temperatures and reaction times in the table, with the reaction yields shown in the table.
Example 3
Prepared according to the procedure for example 1, 4baa in 80% yield.
Example 4
4caa was prepared according to the procedure of example 1 in 74% yield.
Example 5
Prepared according to the procedure for example 1, 4daa in 64% yield.
Example 6
Prepared according to the procedure for example 1, 4eaa in 66% yield.
Example 7
4faa was prepared according to the procedure of example 1 in 62% yield.
Example 8
4gaa was prepared according to the procedure of example 1 in 79% yield.
Example 9
Prepared according to the procedure for example 1, 4haa in 48% yield.
Example 10
4aba was prepared according to the procedure of example 1, in 60% yield.
Example 11
4aca was prepared according to the procedure for example 1 in 59% yield.
Example 12
4ada was prepared in 54% yield according to the procedure of example 1.
Example 13
Prepared according to the procedure for example 1, 4aea in 46% yield.
Example 14
Prepared according to the procedure for example 1, 4iaa in 75% yield.
Since the invention has been described in terms of specific embodiments thereof, certain modifications and equivalent variations will be apparent to those skilled in the art and are intended to be included within the scope of the invention.
Claims (4)
1. A preparation method of a compound shown as a formula IV comprises the step of reacting a compound shown as a formula I, a compound shown as a formula II and a compound shown as a formula III in the presence of a cobalt catalyst,
wherein R is4Selected from hydrogen atom, methyl group, amino group and methoxy groupA group;
R2selected from phenyl, p-methylphenyl, p-methoxyphenyl, p-fluorophenyl and benzyl;
the cobalt catalyst is selected from CoC2O4、CoCl2、Co(acac)2、CoBr2And Co2(CO)8The molar ratio of the compound shown in the formula I to the cobalt catalyst is 1: 0.05-1: 1,
the reaction solvent is acetonitrile and water, the volume ratio of the water to the acetonitrile is 1:10-1:50,
the reaction temperature was 80 ℃.
2. The method according to claim 1, wherein the cobalt catalyst is Co (acac)2。
3. The method according to claim 1, wherein the volume ratio of water to acetonitrile is 1: 20.
4. The method according to claim 1, wherein the molar ratio of the compound represented by formula I, the compound represented by formula II and the compound represented by formula III is 1:2.2: 2.
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