CN103664631B - Preparation method of naftifine hydrochloride - Google Patents
Preparation method of naftifine hydrochloride Download PDFInfo
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- CN103664631B CN103664631B CN201310708291.5A CN201310708291A CN103664631B CN 103664631 B CN103664631 B CN 103664631B CN 201310708291 A CN201310708291 A CN 201310708291A CN 103664631 B CN103664631 B CN 103664631B
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- naftifine hydrochloride
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- naftifungin
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Abstract
The invention provides a preparation method of naftifine hydrochloride, and belongs to the technical field of drug chemical synthesis. The preparation method comprises the following steps: taking 1-naphthoic acid as a starting raw material, in the presence of SOCl2 (Sulfoxide Chloride), reacting with a methylamine water solution to prepare N-methyl-1-naphthamide, enabling the N-methyl-1-naphthamide to react with formaldehyde and styrene in catalysis of Lewis acid in a multicomponent reaction manner to prepare carbonylated naftifine, performing hydrazine hydrate-KOH (Potassium Hydroxide) reduction, acidizing with hydrochloric acid, and separating the compound to obtain the naftifine hydrochloride. Through the cheap Lewis acid catalyzed amine, formaldehyde and styrene three-component one-pot method, the allyl structure unit is constructed in a single step, so that the reaction is greatly simplified, and the yield is improved; the preparation method is free from a noble metal catalyst, so that the production cost of the naftifine hydrochloride is reduced; the raw materials and various reagents are cheap and easy to get, the operation process is simple, the postprocessing procedures are simple, and the preparation method creates good conditions for industrial scale production and commercialization.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of preparation method of naftifine hydrochloride, particularly relate to a kind of with the method for 1-naphthoic acid for starting raw material synthetic hydrochloric acid naftifungin.
Background technology
Naftifine hydrochloride, chemical name: 3-phenyl-2-propylene-N-methyl isophthalic acid-naphthalene methylamine or Bifonazole; English name: English name: Naftifine hydrochloride, 1-Naphthalenemethanamine hydrochloride; CAS:65472-88-0; Molecular formula: C
21h
21n, molecular weight: 287.40, mp 177 DEG C.Be developed by naftifine hydrochloride U.S. MERZ PHARMS, generation Mo in last century 80 goes on the market in the U.S..For Allylamines Desenex.Be applicable to tinea caused by sensitive fungi as tinea pedis and manus, tinea manus and pedis, favus of the scalp, onychomycosis, tinea versicolor, shallow table moniliosis.Its chemical structural formula is as follows:
In numerous synthetic methods of naftifungin, most widely used mainly contains following three kinds of methods: the first passes through transition metal-catalyzed α, the amine alkyl reduction reaction of beta-unsaturated aldehyde and amine; It two is obtained by transition metal-catalyzed lower allyl alcohol and derivative (as acetic ester, halogen, carbonic ether etc.) thereof and the linked reaction of amine; It three is adopt 1-chloronaphthalene methyl to be raw material, makes N-methyl how methylamine after aminated, the latter again with formaldehyde, phenylacetylene condensation, reduction; Or by with formaldehyde, methyl phenyl ketone condensation, reduction reaction, make finally by acidification.These methods comprehensive can be found out, first two method all needs to use the transition metal or hydroborating reagent that price is more expensive, and substrate used needs special preparation method, and the limited source of the substrate such as allyl alcohol or aldehyde; Rear a kind of method steps is various, and complex process is difficult to the variation realizing product structure.
Summary of the invention
The object of the invention is for problems of the prior art, provide a kind of cheaper starting materials to be easy to get, cost is low, and technique is simple, the method for the preparation of industrialization naftifine hydrochloride of easy handling.
The preparation method of naftifine hydrochloride of the present invention is with 1-naphthoic acid for starting raw material, at SOCl
2existence is descended and aqueous methylamine solution reacts obtained N-methylnaphthalene methane amide, make N-methylnaphthalene methane amide and formaldehyde, vinylbenzene under Lewis acid catalysis, carry out the naftifungin that multi-component reaction obtains carbonylation again, then through hydrazine hydrate-KOH reduction, hcl acidifying, be separated, obtain solid phase prod naftifine hydrochloride.Concrete technology is as follows:
(1) synthesis of N-methylnaphthalene methane amide: with 1-naphthoic acid for starting raw material, with acylating reagent SOCl
2with the mol ratio of 1:1.0 ~ 1:2.5, DEG C reaction 3 ~ 8h in room temperature ~ 85, obtained 1-naphthoyl chloride; 1-naphthoyl chloride is aminolysis reaction 5 ~ 12 h in aqueous methylamine solution again, obtains N-methylnaphthalene methane amide;
In aqueous methylamine solution, the consumption of methylamine is 1 ~ 3.5 times of 1-naphthoyl chloride molar weight.
(2) synthesis of the naftifungin of carbonylation: be in organic solvent, under the catalysis of Lewis acid, N-methylnaphthalene methane amide acid amides and formaldehyde, vinylbenzene are with the mol ratio of 1:1:1 ~ 1:5:3.5, in 50 ~ 140 DEG C of reaction 5 ~ 24h, the naftifungin of obtained acidylate---N-methyl-N-allyl group replaces-1-naphthoamide;
Organic solvent adopts THF, toluene, dimethylbenzene, dioxane, DMF, DMSO or dichlorobenzene;
Described Lewis acid is FeCl
3, CuCl
2, TfOH, TFA, I
2, or BF
3oEt
2in a kind of or wherein mixture of two kinds; The consumption of catalyzer Lewis acid is 0.1 ~ 0.5 times of N-methylnaphthalene methane amide molar weight.
(3) synthesis of target product naftifine hydrochloride: in the diethylene glycol solution of hydrazine hydrate-KOH, N-methyl-N-allyl group replaces-1-naphthoamide prior to after 80 ~ 110 DEG C of reduction reaction 1 ~ 5h, then is warming up to 160 ~ 210 DEG C of continuation reactions
1~ 5 h, obtained naftifungin crude product; In the ethyl acetate solution of naftifungin crude product, drip hydrochloric acid, separate out precipitation, suction filtration, filter cake ethyl acetate is washed, and acetate-methanol (V/V=1:0.2 ~ 1:1.2) mixed solvent recrystallization, obtains naftifine hydrochloride.
In the diethylene glycol solution of hydrazine hydrate-KOH, the consumption of hydrazine hydrate is 2 ~ 5 times that N-methyl-N-allyl group replaces-1-naphthoamide molar weight, and the consumption of KOH is 1 ~ 5 times that N-methyl-N-allyl group replaces-1-naphthoamide.
The reaction formula of above-mentioned synthesis is as follows:
Product of the present invention is through the detection such as infrared, nuclear-magnetism, ultimate analysis, and be naftifine hydrochloride sterling, total recovery is more than 60%.
Hinge structure of the present invention has the following advantages:
1, the present invention is by the acid catalyzed amine of cheap Lewis, formaldehyde and vinylbenzene three components one pot reaction, and a step constructs allylic structure unit, enormously simplify reaction, improves productive rate; Without the need to noble metal catalyst, reduce the production cost of naftifine hydrochloride;
2, raw material and all ingredients are all cheap and easy to get, and operating process is simple, and aftertreatment technology is simple, for commercial scale production and commercialization create good condition.
Embodiment
Be described further below by the synthesis of specific embodiment to naftifine hydrochloride of the present invention.
Embodiment 1
(1) N-methyl isophthalic acid-naphthoamide
2synthesis: reference preparation (
eur. J. Org. Chem.2003,2132-2137): N
2under atmosphere, stirring at room temperature, by SOCl
2(4.00 mL, 548.0 mmol) dropwise add 1-naphthoic acid
1(45.6 mmol), gained mixture is heated to 80 DEG C of reaction 2 h; Reaction terminates, the unreacted SOCl of decompression removing
2, residual solution is dissolved in methylene dichloride (4 mL); Add aqueous methylamine solution (46.8 mmol), stirring at room temperature reacts 12 h, then pours reaction solution into saturated NaHCO
3in (500 mL) solution, dichloromethane extraction (3 × 150 mL), merges organic phase, MgSO
4drying, concentrates to obtain N-methyl isophthalic acid-naphthoamide 2, productive rate 92%, mp 159 ~ 160 DEG C.
1H NMR: CDCl
3, 400 MHz. δ (ppm): 8.20 (m, 1 H), 7.81 (m, 2 H), 7.82-7.31 (m, 4 H), 6.37 (br, 1 H), 2.93 (s, 3 H);
13C NMR: CDCl
3, 100 MHz. δ (ppm): 170.2, 134.3, 133.4, 130.2, 129.9, 128.1, 126.8, 126.2, 125.3, 124.7, 125.5, 26.6。
(2) N-methyl-N-allyl group replaces-1-naphthoamide
3synthesis: by N-methyl isophthalic acid-naphthoamide
2(20 mmol), formaldehyde (8 mmol), vinylbenzene (30 mmol), I
2the mixture of (0.4 mmol) and dimethylbenzene (50 mL) is in 110 DEG C of stirring reaction 12 h.Reaction terminates rear liquid and is cooled to room temperature, adds 20% Na
2sO
3the mixed solution of (50 mL) and ethyl acetate (100 mL), is separated organic phase, aqueous phase is extracted with ethyl acetate (3 × 150 mL), MgSO
4drying, concentrated, ethyl alcohol recrystallization, obtains N-methyl-N-allyl group and replaces-1-naphthoamide
3, productive rate 84%.
1H NMR: CDCl
3, 400 MHz. δ (ppm): 8.23 (d, J = 8.1 Hz, 1H), 7.80-7.85 (m, 2H), 7.47-7.15 (m, 9H), 6.50 (d, J = 16.0 Hz, 1H), 6.30 (dt, J = 16.0, J = 6.5 Hz, 1H), 3.20 (d, 1 = 6.5 Hz, 2H), 2.20 (s, 3H).
13C NMR: CDCl
3, 100 MHz. δ (ppm): 165.2, 137.2, 134.9, 133.8, 132.6, 132.4, 128.5, 128.4, 127.9, 127.5, 127.4, 126.3, 126.2, 125.8, 125.5, 125.0, 124.2, 60.0, 42.2。
(3) naftifungin
4synthesis: add successively in single port flask
3(10 mmol) and glycol ether 50 mL, KOH(30 mmol), drip 85% hydrazine hydrate 2.0 mL (65 mmol), drip and finish, in 110 DEG C of reacting by heating 1 h, then change reflux into water distilling apparatus, steam unreacted hydrazine hydrate, be warming up to 160 ~ 180 DEG C, continue return stirring 1.5 h.Be cooled to room temperature, dilute hydrochloric acid is acidified to pH=2, extraction into ethyl acetate (3 × 100 mL), MgSO
4drying, column chromatography purification (hexanes/ethyl acetate 4:1), obtains naftifungin
4.
1H NMR: CDCl
3, 400 MHz. δ (ppm): 8.22 (d, J = 8.1 Hz, 1H), 7.78-7.88 (m, 2H), 7.47-7.17 (m, 9H), 6.50 (d, J = 16.0 Hz, 1H), 6.30 (dt, J = 16.0, J = 6.5 Hz, 1H), 3.87 (s, 2H), 3.20 (d, 1 = 6.5 Hz, 2H), 2.20 (s, 3H).
13C NMR: CDCl
3, 100 MHz. δ (ppm): 137.0, 134.7, 133.8, 132.6, 132.4, 128.5, 128.4, 127.9, 127.5, 127.4, 127.3, 126.2, 125.8, 125.5, 125.0, 124.5, 60.3, 60.0, 42.4. MS(CI): 288 (M+1), 287 (M)。
(4) naftifine hydrochloride
5synthesis: above-mentioned naftifungin is dissolved in 100 mL ethyl acetate, ethyl acetate solution 10 mL(m/m:8% of instillation HCl is stirred) at 0 DEG C, stirring reaction 2 h, separate out precipitation, suction filtration, filter cake cold ethyl acetate washing (10 mL), with acetate-methanol (V/V=1:1) mixed solvent recrystallization, obtains naftifine hydrochloride
5.(3), the total recovery 80% of (4) two-step reaction, the total recovery 61.6% of naftifine hydrochloride.mp 175～177 ℃。
1H NMR: CDCl
3, 400 MHz. δ (ppm): 8.29-8.16 (m, 1H), 7.91-7.80 (m, 2H), 7.62-7.32 (m, 9H), 6.51(d, J = 18 Hz, 1H), 5.82 (dt, 1H, J=18Hz, 7.5Hz), 3.88 (s, 2H), 3.20 (d, 2H, J = 7.5HZ), 2.22 (s, 3H);
13C NMR: CDCl
3, 100 MHz. δ (ppm): 137.0, 134.7, 133.8, 132.6, 132.4, 128.5, 128.4, 127.9, 127.5, 127.4, 127.3, 126.2, 125.8, 125.5, 125.0, 124.5, 60.3, 60.0, 42.4。
Embodiment 2
(1) N-methyl isophthalic acid-naphthoamide
2synthesis: with embodiment 1.
(2) N-methyl-N-allyl group replaces-1-naphthoamide
3synthesis: catalyzer is FeCl
3(20% mmol), solvent xylene changes THF(50 mL into), temperature of reaction is 140 DEG C, and the reaction times is 5h, and other is identical with embodiment 1.N-methyl-N-allyl group replaces-1-naphthoamide
3productive rate be 83%.
(3) naftifungin
4synthesis: react on 80 DEG C of reacting by heating 5h; Steam unreacted hydrazine hydrate, be warming up to 180 ~ 210 DEG C, continue reaction 1 h, the other the same as in Example 1.
(4) naftifine hydrochloride
5synthesis: with embodiment 1.Naftifine hydrochloride overall yield is 60.8%.
Embodiment 3
(1) N-methyl isophthalic acid-naphthoamide
2synthesis: with embodiment 1.
(2) N-methyl-N-allyl group replaces-1-naphthoamide
3synthesis: catalyzer is BF
3oEt
2(20% mmol), solvent xylene changes dioxane (50 mL) into, and temperature of reaction is 50 DEG C, and the reaction times is 24h, and other is identical with embodiment 1.N-methyl-N-allyl group replaces-1-naphthoamide
3productive rate be 85.5%.
(3) naftifungin
4synthesis: KOH:20 mmol), 85% hydrazine hydrate dripping quantity 2.0 mL (65 mmol), reacts on 95 DEG C of reacting by heating 3h; Steam unreacted hydrazine hydrate, be warming up to 190 ~ 200 DEG C, continue reaction 3 h, the other the same as in Example 1.
(4) synthesis of naftifine hydrochloride 5: with embodiment 1.Naftifine hydrochloride overall yield is 62.5%.
Claims (10)
1.
oneplanting the method preparing naftifine hydrochloride, is with 1-naphthoic acid for starting raw material, at SOCl
2existence is descended and aqueous methylamine solution reacts obtained N-methylnaphthalene methane amide, N-methylnaphthalene methane amide and formaldehyde, vinylbenzene carry out the naftifungin that multi-component reaction obtains acidylate under Lewis acid catalysis, then through hydrazine hydrate-KOH reduction, hcl acidifying, be separated, obtain solid phase prod naftifine hydrochloride;
The structural formula of the naftifungin of acidylate is:
Structural formula through hydrazine hydrate-KOH reduzate is:
。
2. prepare the method for naftifine hydrochloride as claimed in claim 1, it is characterized in that: the synthesis technique of N-methylnaphthalene methane amide is: with 1-naphthoic acid for starting raw material, with acylating reagent SOCl
2with the mol ratio of 1:1.0 ~ 1:2.5, reaction 3 ~ 8h at room temperature to 85 DEG C, obtained 1-naphthoyl chloride; 1-naphthoyl chloride is aminolysis reaction 5 ~ 12 h in aqueous methylamine solution again, obtains N-methylnaphthalene methane amide.
3. prepare the method for naftifine hydrochloride as claimed in claim 2, it is characterized in that: in aqueous methylamine solution, the amount of methylamine is 1 ~ 3.5 times of 1-naphthoyl chloride molar weight.
4. prepare the method for naftifine hydrochloride as claimed in claim 1; it is characterized in that: the synthesis technique of the naftifungin of described acidylate; in organic solvent; under the catalysis of Lewis acid; N-methylnaphthalene methane amide and formaldehyde, vinylbenzene are with the mol ratio of 1:1:1 ~ 1:5:3.5; in 50 ~ 140 DEG C of reaction 5 ~ 24h, the naftifungin of obtained acidylate.
5. prepare the method for naftifine hydrochloride as claimed in claim 4, it is characterized in that: described organic solvent is THF, toluene, dimethylbenzene, dioxane, DMF, DMSO or dichlorobenzene.
6. as described in claim 4 or 5, prepare the method for naftifine hydrochloride, it is characterized in that: described Lewis acid is FeCl
3, CuCl
2, TfOH, TFA, I
2, or BF
3oEt
2in a kind of or wherein mixture of two kinds.
7. prepare the method for naftifine hydrochloride as claimed in claim 6, it is characterized in that: the consumption of catalyzer Lewis acid is 0.1 ~ 0.5 times of N-methylnaphthalene methane amide molar weight.
8. prepare the method for naftifine hydrochloride as claimed in claim 1; it is characterized in that: the preparation technology of target product naftifine hydrochloride: in the diethylene glycol solution of hydrazine hydrate-KOH; the naftifungin of acidylate prior to after 80 ~ 110 DEG C of reaction 1 ~ 5h, then is warming up to 160 ~ 210 DEG C of continuation reactions
1~ 5 h, obtained naftifungin crude product; In the ethyl acetate solution of naftifungin crude product, drip concentrated hydrochloric acid, separate out precipitation, suction filtration, filter cake ethyl acetate is washed, and acetate-methanol mixed solvent recrystallization, obtains naftifine hydrochloride.
9. prepare the method for naftifine hydrochloride as claimed in claim 8, it is characterized in that: in the diethylene glycol solution of hydrazine hydrate-KOH, the consumption of hydrazine hydrate is 2 ~ 5 times of the naftifungin molar weight of acidylate, and the consumption of KOH is 1 ~ 5 times of the naftifungin of acidylate.
10. prepare the method for naftifine hydrochloride as claimed in claim 8, it is characterized in that: in acetate-methanol mixed solvent, the volume ratio of ethyl acetate and methyl alcohol is 1:0.2 ~ 1:1.2.
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| CN113277963B (en) * | 2021-06-02 | 2022-11-04 | 南京工业大学 | Amine compound and preparation method and application thereof |
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