CN108484471A - A kind of aerosol type one-pack type hair dye for the compound of hair dyeing and comprising it - Google Patents
A kind of aerosol type one-pack type hair dye for the compound of hair dyeing and comprising it Download PDFInfo
- Publication number
- CN108484471A CN108484471A CN201810320906.XA CN201810320906A CN108484471A CN 108484471 A CN108484471 A CN 108484471A CN 201810320906 A CN201810320906 A CN 201810320906A CN 108484471 A CN108484471 A CN 108484471A
- Authority
- CN
- China
- Prior art keywords
- compound
- hair
- formula
- raw material
- hair dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
- A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Chemistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to a kind of compound for hair dyeing and comprising its aerosol type one-pack type hair dye, there is the structural formula as shown in formula I or formula II：Wherein, the X in formula II is Br or Cl.The advantageous effect of raw material compound provided by the invention is：1) new raw material is easy to penetrate into hair, autoxidation polymerize in air inside hair, the melanin for generating nature black plays coloring, have the advantages that coloring is fast, coloring is lasting, the melanin generated is polymer, melanin itself is the substance of human body melanocyte production, and inside of human body will not be inversely entered in hair.2) new raw material and hair dye provided by the invention have good coloring, especially have universality, can the human hair of a variety of colors such as white, canescence, faint yellow, golden yellow, red be dyed nature black.
Description
Technical field
The present invention relates to a kind of new raw materials and its aerosol type one-pack type hair dye for hair dyeing, belong to special cosmetics technology neck
Domain.
Background technology
Hair dyeing is by increasing or decreasing the various pigments in hair, to reach the process for changing hair color；Hair dyeing
Agent is the cosmetics for the specific use for referring to change hair color, hair being dyed to the different depth different colours of color.According to
The duration of hair dyeing color and luster is different, and hair dye can be divided into temporary, semi-persistent and permanent hair color；Wherein, persistence contaminates
Hair agent is the major demands in market.
Primary raw material used in permanent hair color is the dyestuff or pigment for playing coloration, these raw materials include natural
Dyestuff, metal dye and organic synthetic dye.Safety and coloring of the property of raw material used in hair dye to hair dye
Play the role of conclusive.Natural hair dyeing raw material, such as garden balsam, yellow chamomile and hematoxylin etc., mainly carry from plant
The organic substance of acquisition is taken, toxicity is low, safe to use, but dyeing time is not lasting enough, effect is still poor.Metal dye is mostly
The salt or oxide of the metals such as lead, iron, copper, cobalt, wherein metal ion can occur with the sulphur of the disulfide bond in hair keratin
Reduction reaction and generate black；Common metal hair dyeing raw material have lead acetate, bismuth citrate, silver nitrate, copper sulphate, copper chloride,
Cobalt nitrate, iron chloride, ferric sulfate and ferrous sulfate etc.；Although such hair dyeing raw material is more early applied, toxicity is big, dangerous.
Organic synthetic dye is a kind of important hair dye raw material；According to the chemical change occurred in hair dye, persistently
Property organic synthesis hair dyeing raw material be divided into as oxidation dye, reducing dye and imitative natural black pigment dyestuff.Oxidation dye is synthesis dye
Coloring hairs, and most widely used permanent hair color raw material at present are used in material earliest；The composition one of oxidation dye
As be made of color developing agent, coupling agent and oxidant three parts；The mechanism of action is in hair dye, and color developing agent is acted in oxidant
Under be oxidized into dyestuff intermediate, the intermediate and coupling agent generate color and have hair dyed after coupling reaction occurs.Color developing agent master
If phenylene diamine compound, for example, p-phenylenediamine, to toluenediamine, to ammonia diphenylamines, chlorination p-phenylenediamine, m-phenylene diamine (MPD),
Toluylenediamine, o-phenylenediamine and ortho-toluene diamine etc.；But these compounds all have very strong anaphylaxis and the secondary work of poison
With majority, which has been put into, is forbidden to use list.Coupling agent is also referred to as colour coupler, mainly hydroquinone, resorcinol, right
The compounds such as amino-phenol, m-aminophenol, o-aminophenol, pyrogaelol, alpha- naphthols；These mass pigmentations compared with
Securely, but there is toxic side effect more, and there is irritation, easily cause skin allergy；Although being put into cosmetics uses mesh
Record, but mostly regulated substance.Oxidant is mainly hydrogen peroxide (also known as hydrogen peroxide), and the hydrogen peroxide of concentration 30~35% is water-soluble
Liquid, oxidisability is strong, property is unstable, easy decomposition, and not only there are security risks for storage, and stimulates the skin of people, causes allergy
Deng reaction.Therefore, there is strong toxic side effect, stimulation and allergy etc. to lack for the permanent hair color that prepared by many oxidation dyes
Point.
Reducing dye in organic synthetic dye generally comprises two components, developing dye body and alkaline reducer.In recent years
Come, France and Japan have developed coloring hairs anthraquinone, benzoquinones series of reductions leuco dye, and when use can need not coordinate reduction
Agent.Reducing dye as oxidation dye, prepared permanent hair color there is toxic side effect possessed by dyestuff itself,
The shortcomings of stimulation and allergy.
The effects that toxic side effect, carcinogenicity, allergy and stimulation, is the factor for the most critical for restricting hair dye market, therefore opens
It is the real demand of users and market to send out hair dye safe and efficient.Since pigment raw material is hair dye safety and is had
The most important source of effect property, therefore, the exploitation of safe and efficient hair dye new raw material is most important；One of direction is
It is that the inherent biological effect mechanism formed according to human body or organism itself color development and the colour of skin is designed and development.
Natural black pigment (melanin) is a kind of endogenic substance being widely present in organism, in animal body
Black disorderly and black human hair is all by the biochemical catalytic action of the copper tyrosinase in melanocyte, by the ammonia of phenolic hydroxy group
Base acid is that raw material carries out being converted into melanin precursor (or presoma) small molecule, and then is polymerized to melanin polymer so that people
Black is presented in hair, the colour of skin of people and the animal body colour of skin.
According to the biomechanism that melanin is formed, the companies such as Japanese Kao and L'Oreal, France are in nineteen nineties
It begins one's study and utilizes the new raw material of melanin precursor (or presoma) small molecule exploitation hair dye and production, the corresponding hair dyeing of listing
Agent.European patent EP 0530229B1 takes the lead in reporting 5,6- dihydroxy indoles quinoline (or 5,6- dihydroxy indoline) and its spread out
Biology is used as dyeing raw material；Chinese patent CN1196463C and CN1216591C report 5,6- dihydroxy indole quinolines within 2005
(or 5,6- dihydroxy indoline) and its derivative, the multicomponents such as 5,6- dihydroxy indoles and its derivative are former as dyeing
Material.Wherein, the chemical structural formula of 5,6- dihydroxy indoles quinoline derivant and 5,6- dihydroxy indole derivatives is as follows：
Hair dye prepared by this dyeing raw material this have the advantage that, natural hair dye melanocyte is applied on hair, is made
It uses the oxygen in air to be dyed as unique oxidant, generates similar natural color.The disadvantage is that each pigment raw material pair
The coloured color development of original and hair quality of the people answered is single, that is, each pigment raw material must find the color development to match and could reach
To relatively satisfactory effect；For example, when using the hair dye of the dihydroxy indole quinoline Han 5,6-, needing to be used for multiple times can just make
People with grey hair has natural color development again.Hair can use indoline in the natural light golden yellow people to brown
(or indoline) is used as unique dyestuff former；But in hair in natural red, especially dark, grey to black
People is in use, being used together and could be enabled often only by with other dye components (especially oxidation dye precursors)
The effect of people's satisfaction.That is, the universality of these dyeing raw materials is too poor.In addition, colorability when dyeing is weaker, need
Repeated multiple times dyeing, can be only achieved expected effect.
Therefore, a kind of universality that can improve melanin precursor dyestuff is developed, coloring effect is improved and accelerates dyeing speed
Degree, while keeping the safety of hair dye raw material and hair dye new raw material the advantages that oxygen is as oxidant using in air becomes
This field technical problem urgently to be resolved hurrily.
Invention content
Deficiency present in melanin precursor dyestuff of the present invention for the prior art provides a kind of for the novel of hair dyeing
Compound and aerosol type one-pack type hair dye comprising the compound.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of compound for hair dyeing has the structural formula as shown in formula I or formula II：
Wherein, the X in formula II is Br or Cl.
The preparation method of above compound is as follows：
1) it is raw material with compound 1, in inert atmosphere, heating reflux reaction under the action of alkali carbonate obtains
To compound 2；Compound 1 can be according to document, with commercially available 3,4- dimethoxy-phenylethylamines for raw material, by trifluoroacetyl group
After acylation reaction, obtained with Iod R；
2) it is raw material with compound 2, in air or oxygen atmosphere, is stirred to react at room temperature 16~24 hours, generates two
The monocrystalline X-ray diffraction figure of dimmer compound 3, compound 3 is as shown in Figure 1；
3) it is raw material with compound 3, under inert atmosphere and stirring condition, Boron tribromide is added dropwise into raw material, was added dropwise
At -60 DEG C hereinafter, being reacted in -40 DEG C or less after being added dropwise, demethylating protecting group obtains shown in formula I control system temperature in journey
Compound；
Reaction route is as follows：
Further, compound shown in formula I can obtain compound shown in formula II by the following method, by compound shown in formula I
It is placed in hydrogen bromide solution or hydrogen chloride solution, is stirred to react in the environment of 0 DEG C to room temperature, obtain compound shown in formula II, instead
Answer process as follows：
Further, above-mentioned hydrogen bromide solution specifically refers to aqueous solution of hydrogen bromide or hydrogen bromide in organic solvent molten
Liquid, hydrogen chloride solution refer to the solution of hydrochloric acid or hydrogen chloride in organic solvent (such as methanol, dioxane).
Further, alkali carbonate and the molar ratio of compound 1 are preferably 2 in step 1)：1, tribromide in step 3)
Boron and the molar ratio of compound 3 are preferably 5：1.
In actual mechanical process, first step reaction and second step reaction two-step reaction can be merged into the step treated different things alike
Reaction is completed, i.e., is raw material with compound 1, in inert environments, in alcohol organic solvent (such as methanol, ethyl alcohol, isopropanol
Deng) in, under being acted on alkali carbonate (such as potassium carbonate, cesium carbonate etc.), it is heated to reflux to raw material and is fully converted to chemical combination
It after object 2, is cooled to room temperature, continues to be stirred to react, centre is not required to detach, you can finally obtain compound 3.With chemical equation table
Show as follows：
The advantageous effect of raw material compound provided by the invention is：
1) new raw material is easy to penetrate into hair, and autoxidation polymerize in air inside hair, generates nature black
Melanin plays coloring, has the advantages that coloring is fast, coloring is lasting, the melanin generated is polymer, melanin sheet
Body is the substance of human body melanocyte production, and inside of human body will not be inversely entered in hair.
2) new raw material provided by the invention has good coloring, especially has universality, can be by white, ash
The human hair of a variety of colors such as white, faint yellow, golden yellow, red dyes nature black.
3) new raw material is stablized in aqueous solution under closing (must not ingress of air or oxygen) state；The hair dyeing of preparation
Agent can place for a long time, enabled again after placing for 2 years, do not influence hair dyeing effect.
The one-pack type that the present invention is also claimed comprising compound shown in above-mentioned formula I or formula II as melanin precursor is had hair dyed
Agent.
Further, the dosage of melanin precursor is 0.5~10wt% in the aerosol type one-pack type hair dye.
Further, the aerosol type one-pack type hair dye includes following component：0.5~10wt% of melanin precursor, lipid 2~
12wt%, 2~5wt% of surfactant, 0.1~0.5wt% of antioxidant, 1~10wt% of alkaline agent, thickener 0.1~
1.0wt%, 1~10wt% of organic solvent, surplus are water.
Further, the lipid refers to 1,3-BDO, glycerine, grape seed oil, rapeseed oil, castor oil, the fat of C12~18
The fatty alcohol of fat alcohol, C16~18, cetylstearyl alcohol, isopropyl palmitate, isopropyl myristate, synthesis saualane, list
The compounding of any one or two kinds or more in tristerin, the fatty alcohols of preferably C12~18, the fatty alcohols of C16~18, ten
Six alkyl octadecanols.
Further, the alkaline agent refers to any one in monoethanolamine, histidine, arginine or two kinds or more
Compounding, preferably arginine, the pH for adjusting hair dye are 8.5~9.5.
Further, the antioxidant refers to any one in ascorbic acid, arabo-ascorbic acid, sodium sulfite or two kinds
Or more compounding, preferred ascorbic acid.
Further, the surfactant refers to that ceteareth series, stearine, polyoxyethylene -2 are hard
The compounding of any one or two kinds or more in the stearic alcohol ether of lipidol ether, polyoxyethylene -21, preferably glycerine stearate, institute
It refers to any one in hydroxyethyl cellulose, xanthans, chitosan, preferably hydroxyethyl cellulose to state thickener.
Further, the organic solvent refer to 75% or more ethyl alcohol of concentration, ethylene glycol, glycerine, ethane, propane, butane,
Dimethyl ether or propylene oxide.When preparing hair dye finished product, when especially cream rinse is as dosage form, hydraulic pressure second is preferably selected
Alkane, hydraulic pressure propane or hydraulic pressure propylene oxide.
The advantageous effect of aerosol type one-pack type hair dye provided by the invention is：
1) dyeing raw material principal component is single in aerosol type one-pack type hair dye of the invention, it is not necessary that other color developing agents and coupling is added
Agent, in dyeing course, the oxygen in air is unique oxidant, need not be added with strong oxidizing property, strong and stimulating, be easy to
Other oxidants such as hydrogen peroxide of decomposition, therefore there is no any stimulation, safe without toxic side effect to human body；
2) dyeing raw material in hair dye of the invention is easy to penetrate into hair, in air from oxygen inside hair
Change polymerization, the melanin for generating nature black plays coloring, is dyed using endogenous material, and, coloring fast with coloring is held
Long advantage, the melanin generated are polymer, and melanin itself is the substance of human body melanocyte production, will not be in head
Inversely enter inside of human body in hair, ensure that safety of the hair dye to human body；
3) hair dye of the invention has good coloring, especially has universality, can will white, greyish white
The human hair of a variety of colors such as color, faint yellow, golden yellow, red dyes nature black.
Description of the drawings
Fig. 1 is the monocrystalline X-ray diffraction figure of compound 3；
Specific implementation mode
Principles and features of the present invention are described below in conjunction with example, the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the present invention.
In following examples, Nuclear Magnetic Resonance uses Varian Mercury 400MHz types test compound1H-
NMR, chemical shift are indicated using δ (ppm)；Mass spectrograph using Agilent 1100 LC-MS measure compound molecular weight and
The molecular ion peak of feature；High-efficient liquid phase analysis instrument carries out reaction tracking, purity point using Agilent Agilent HPLC systems
Analysis；In hair dye formulas relative amount with weight percent (wt%) be measurement standard.
One, the preparation method of compound shown in formula I and formula II
Embodiment 1：
The preparation method of compound, includes the following steps shown in a kind of formula I：
1) 2,5,6- dimethoxy indoline of compound is synthesized；Chemical equation is：
Experimental procedure and operation are：Magnetic agitation and constant pressure funnel are installed in the three neck round bottom flask of 1L, it is built-in
Glass-stem thermometer.Under nitrogen protection, 40.3 grams of (0.1mol) compounds 1 and 300mL methanol is added into flask successively；It opens
Stirring is opened, at 25~26 DEG C of room temperature, 27.6 grams of (0.2 mol, 2.0eq.) potassium carbonate are added；Reflux state is then heated to,
And it maintains to be stirred to react 6~8 hours at this temperature.TLC shows that raw material all disappears.
Reaction system is cooled to room temperature, solvent is boiled off with Rotary Evaporators reduced pressure, obtains solid residue；Then
400mL dichloromethane is added, is vigorously stirred, mashing continues 10 minutes so that product is substantially dissolved in dichloromethane.Filtering,
Obtain filtrate；Saturated sodium bicarbonate aqueous solution (100mLx1), saturated salt solution (100mLx1) is used to wash successively, anhydrous magnesium sulfate
It is dry.Filtering, obtains clear filtrate.
It is concentrated under reduced pressure with Rotary Evaporators, boils off solvent, obtain solid residue, weighed 18 grams, yield 99%；Crude product
It can be not required to detach, be directly used in and react in next step.
Product English name：5,6-dimethoxyindoline；Chinese：5,6- dimethoxy indolines；Analyze number
According to：1H-NMR (400MHz, CDCl3):δ (ppm)=6.727 (s, 1H, Ar-H), 6.239 (s, 1H, Ar-H), 5.067 (s, 1H,
), NH 3.656 (s, 3H, OCH3), 3.616 (s, 3H, OCH3), 3.370~3.333 (m, 2H, CH2), 2.830~2.787 (m,
2H,CH2).HPLC:The purity that 254nm is measured is 98%；LCMS：Found 180.2([M+H]+)；C10H13NO2,MW
calcd.179.22.
2) compound 3,5- (5,6-dimethoxyindolin-1-yl) -6-methoxy-1H-indole are synthesized；Chemistry
Equation is：
Experimental procedure and operation are：At room temperature, 18 g of compound 2 are dissolved in 200mL acetonitriles, are contacted in container opening
Air is passed through in the environment of oxygen, is vigorously stirred；And sustained response, TLC tracking reaction to raw material completely disappear, about
Need 16-24 hours.It is concentrated under reduced pressure to give crude product with Rotary Evaporators；It is isolated and purified with silica gel column chromatography, leacheate
For petroleum ether-ethyl acetate (90:10, v/v) it is clear crystal, to obtain compound 3；It is placed in receiving bottle and monocrystalline is precipitated.Change
It is 11.5 grams to close 3 weight of object, yield 71% (two-step reaction gross production rate).
Product title：5-(5,6-dimethoxyindolin-1-yl)-6-methoxy-1H-indole；Analyze data：
1H-NMR (400MHz, CDCl3):δ (ppm)=8.154 (s, 1H, Ar-H), 7.684 (s, 1H, Ar-H), 7.115 (d, 1H, J
=2.8Hz, CH), 6.965 (s, 1H, Ar-H), 6.795 (s, 1H, Ar-H), 6.441 (dd, 1H, J=2.8Hz, 1.6Hz,
NCH),6.161(s,1H,NH),3.938(s,3H,OCH3), 3.869(s,3H,OCH3),3.80-3.74(m,2H,CH2),
3.689(s,3H,OCH3),3.15(br s,2H, CH2).HPLC:The purity that 254nm is measured is 95%；LCMS：Found
324.2([M+]), 325.2([M+H]+)；C19H20N2O3,MW calcd.324.38.
3) compound, chemical equation shown in 3 formula I of compound are：
Experimental procedure and operation are：Under room temperature (25 DEG C), 32.4 grams of (0.1mol) compounds 3 are dissolved in 500mL dichloros
In methane, stirred under nitrogen atmosphere；It is cooled to -78 DEG C.48mL (0.5mol, 5.0eq.) tribromo is added dropwise by constant pressure funnel
The mixed solution for changing boron and 122mL dichloromethane during dropwise addition, keeps reaction temperature to be less than -60 DEG C.After being added dropwise ,-
40 DEG C or less the reaction was continued 1 hour；Then, it is to slowly warm up to room temperature, the reaction was continued 2 hours；TLC shows that raw material completely disappears.
Reaction system is warming up to 0 DEG C, then, the sodium hydroxide that 300mL 4mol/L are added dropwise with vigorous stirring is water-soluble
Liquid；After being added dropwise, continue to be vigorously stirred 30 minutes.At this point, strong basicity is presented in system.Then, at 0 DEG C, 4mol/L is added dropwise
Aqueous hydrochloric acid solution, the acid-base property of regulation system to pH=3~5.It stirs after ten minutes, stratification.Organic phase is eaten with saturation
Salt washes (160mLx1), and anhydrous magnesium sulfate dries (200 grams of x1), filters, obtains clear dichloromethane solution.It is steamed with rotation
Send out instrument be concentrated under reduced pressure, obtained crude product be off-white powder, big and heavy 25 grams.25 grams of crude products are mixed with 100mL ethyl acetate
Close, heating recrystallized, obtain white solid be compound of formula I, 22.8 grams, yield 80%.
Product chemistry title：1-(6-hydroxy-1H-indol-5-yl)indoline-5,6-diol；Analyze data：
1H-NMR (400MHz, DMSO-d6):δ (ppm)=10.25 (s, 1H, NH), 10.12 (s, 1H, ArOH), 9.50 (br s, 2H,
), ArOHx2 7.18 (s, 1H, Ar-H), 7.08 (d, 1H, J=8.4Hz), 6.93 (s, 1H, Ar-H), 6.56 (d, 1H, J=
8.4Hz),6.53(s,1H,Ar-H),6.48(s,1H,Ar-H), 4.18(m,2H),2.98(m,2H).HPLC:254nm is measured
Purity be 100%；LCMS：Found 283.2([M+H]+)；C16H14N2O3,MW calcd.282.30.
Embodiment 2：
The preparation method of compound, includes the following steps shown in a kind of formula I：
1) method treated different things alike directly synthesizes compound 3 by compound 1, and chemical equation is：
Experimental procedure and operation are：Magnetic agitation and constant pressure funnel are installed in the three neck round bottom flask of 1L, it is built-in
Glass-stem thermometer.Under nitrogen protection, 40.3 grams of (0.1mol) compounds 1 and 300mL methanol is added into flask successively；It opens
Stirring is opened, at 25~26 DEG C of room temperature, 27.6 grams of (0.2 mol, 2.0eq.) potassium carbonate are added；Reflux state is then heated to,
And it maintains to be stirred to react 6-8 hours at this temperature.TLC shows that raw material all disappears.
(25 DEG C) are cooled to room temperature, by reaction system opening, air is accessed or is passed through in the environment of oxygen, acutely stir
It mixes；Sustained response, to intermediate 5,6- dimethoxy indolines completely disappear, and take around 16~24 hours for TLC tracking reactions.
It is concentrated under reduced pressure to give solid residue with Rotary Evaporators；Then 400mL dichloromethane is added, is vigorously stirred, mashing continues 10
Minute so that product is substantially dissolved in dichloromethane.Filtering, obtains filtrate；Saturated sodium bicarbonate aqueous solution is used successively
(100mLx1), saturated salt solution (100mLx1) are washed, anhydrous magnesium sulfate drying.Filtering, obtains clear filtrate.
It is concentrated under reduced pressure with Rotary Evaporators, boils off solvent, obtain solid residue.With silica gel column chromatography detach pure
Change, leacheate is petroleum ether-ethyl acetate (90:10, v/v) it is clear crystal, to obtain compound 3；Analysis is placed in receiving bottle
Go out solid or monocrystalline.3 weight of compound is 12.2 grams, yield 75%.The analysis data consistent with Example 1 of compound 3.
2) compound, chemical equation shown in 3 formula I of compound are：
Experimental procedure and operation are：Under room temperature (25 DEG C), 32.4 grams of (0.1mol) compounds 3 are dissolved in 500mL dichloros
In methane, stirred under nitrogen atmosphere；It is cooled to -78 DEG C.48mL (0.5mol, 5.0eq.) tribromo is added dropwise by constant pressure funnel
The mixed solution for changing boron and 122mL dichloromethane during dropwise addition, keeps reaction temperature to be less than -60 DEG C.After being added dropwise ,-
40 DEG C or less the reaction was continued 1 hour；Then, it is to slowly warm up to room temperature, the reaction was continued 2 hours；TLC shows that raw material completely disappears.
Reaction system is warming up to 0 DEG C, then, the sodium hydroxide that 300mL 4mol/L are added dropwise with vigorous stirring is water-soluble
Liquid；After being added dropwise, continue to be vigorously stirred 30 minutes.At this point, strong basicity is presented in system.Then, at 0 DEG C, 4mol/L is added dropwise
Aqueous hydrochloric acid solution, the acid-base property of regulation system to pH=3~5.It stirs after ten minutes, stratification.Organic phase is eaten with saturation
Salt washes (160mLx1), and anhydrous magnesium sulfate dries (200 grams of x1), filters, obtains clear dichloromethane solution.It is steamed with rotation
Send out instrument be concentrated under reduced pressure, obtained crude product be off-white powder, big and heavy 25 grams.25 grams of crude products are mixed with 100mL ethyl acetate
Close, heating recrystallized, obtain white solid be compound of formula I, 22.8 grams, yield 80%.
Embodiment 3：
A method of hydrobromate shown in formula II, chemical equation is obtained by the reaction with hydrobromic acid in the compound shown in formula I
For：
Experimental procedure and operation are：The hydrobromic acid aqueous solution for measuring 20mL 40wt%, is transferred in 50mL round-bottomed flasks,
Magneton is added, 0 DEG C is cooled under stirring；Then, 7.05 grams of (25mmol) compound of formula I are added；It is stirred 30 minutes at 0 DEG C
After warm naturally to room temperature (25 DEG C), continue stirring 2 hours.Under stiring, it is gradually added into and to pre-cool into reaction system
Dioxane 200mL, product are gradually precipitated；After mashing state is presented in system, continue stirring 10 minutes.It stands, filtering obtains shallow
Brown solid, as hydrobromate product.It is 4-6 hours dry at 50 DEG C in vacuum drying chamber, it weighs 8.9 grams, yield
98%.
Analyzing data is：The purity measured under 254nm is 100%；Elemental analysis result：C, 52.90%, H, 4.17%,
Br, 21.98%；N, 7.71%, O, 13.23%.
Embodiment 4：
A method of hydrogen chlorate shown in formula II, chemistry side is obtained by the reaction with hydrogen chloride solution in the compound shown in formula I
Formula is：
Experimental procedure and operation are：The methanol solution for measuring the hydrogen chloride of 25mL 4mol/L is transferred to 50mL round bottoms burning
In bottle, magneton is added, 0 DEG C is cooled under stirring；Then, 7.05 grams of (25mmol) compound of formula I are added；30 are stirred at 0 DEG C
Room temperature (25 DEG C) is warmed naturally to after minute, continues stirring 2 hours.Under stiring, it is gradually added into reaction system cold in advance
But dioxane 200mL, product are gradually precipitated；After mashing state is presented in system, continue stirring 10 minutes.It stands, filtering obtains
To off-white powder, as hydrogen chlorate's product.It is 4~6 hours dry at 50 DEG C in vacuum drying chamber, it weighs 7.9 grams, yield
99%.
Analyzing data is：The purity measured under 254nm is 100%；Elemental analysis result：C, 60.30%, H, 4.75%,
Cl, 11.12%；N, 8.78%, O, 15.09%.Analysis result is consistent with theoretical calculation.
A kind of aerosol type one-pack type hair dye
Embodiment 1：
Aerosol type one-pack type hair dye formula：Compound of formula I is as melanin precursor 8.0%；Lipid C12-18 fatty alcohols 4%, it is single
Tristerin 6%, cetylstearyl alcohol 2%；Glycerol stearate ester surfactant 2%；Ascorbic acid is anti-oxidant
Agent 0.3%；Arginine alkaline agent (it is 9.0 to adjust pH) 3%；95% ethyl alcohol organic solvent, 10%；Hydroxyethyl cellulose thickens
Agent, 0.2%；Deionized water surplus.
Embodiment 2：
Aerosol type one-pack type hair dye formula：Compound of formula I is as melanin precursor 10.0%；Cetylstearyl alcohol 2%,
C16-18 fatty alcohols 6.7% synthesize saualane 2%；, the stearic ether surfactants of polyoxyethylene -21 3%；Sodium sulfite is anti-
Oxidant 0.5%；Histidine alkaline agent (it is 9.0 to adjust pH) 5%；95% ethyl alcohol organic solvent, 3%；Xanthans thickener,
0.4%；Deionized water surplus.
Embodiment 3：
Aerosol type one-pack type hair dye formula：Compound of formula I is as melanin precursor (or presoma) 2.0%；Lipids Palmitic acid is different
Propyl ester 1%, grape seed oil 4%, cetylstearyl alcohol 1%；- 2 tristearin ether surfactants 2% of polyoxyethylene；It is anti-bad
Hematic acid antioxidant 0.1%；Arginine alkaline agent (it is 9.0 to adjust pH) 1%；Hydraulic pressure propane organic solvent, 8%；Chitosan increases
Thick dose, 0.1%；Deionized water surplus.
Embodiment 4：
Aerosol type one-pack type hair dye formula：The hydrobromate of compound of formula I is as melanin precursor (or presoma) 0.5%；Fat
Matter cetylstearyl alcohol 2%；Glycerol stearate ester surfactant 2%；Arabo-ascorbic acid is as antioxidant 0.2%；
Monoethanolamine is as alkaline agent (adjust pH be 9.0), and 8%；95% ethyl alcohol organic solvent, 1%；Hydroxyethylcellulose thickener,
0.5%；Deionized water surplus.
Embodiment 5：
Aerosol type one-pack type hair dye formula：The hydrobromate of compound of formula I is as melanin precursor (or presoma) 5.0%；Fat
Matter C12-18 fatty alcohols 2%, 1,3-BDO 6.7%, glycerine 2%；Ceteareth surfactant 5%；Vitamin C
Sour antioxidant 0.3%；Arginine alkaline agent (it is 9.0 to adjust pH), 10%；Hydraulic pressure ethylene oxide organic solvent, 4%；Hydroxyl second
Base cellulose thickener, 1.0%；Deionized water surplus.
We have carried out following test to the hair dye of embodiment 1-5：
The hair dye hair cream that we are formulated using embodiment 1-5, respectively to white, canescence, faint yellow, golden yellow and red
The human hair of five kinds of colors such as color is dyed；
1) rubbing after five minutes, the foam for removing hair surface is eluted with clear water；As a result, the hair of all colours is all contaminated
At natural black.
2) rubbing after ten minutes, the foam for removing hair surface is eluted with clear water；As a result the hair of all colours is all contaminated
At corvinus.In dyeing course, no peculiar smell the skin being in direct contact such as does not stimulate and uncomfortable feels.Illustrate these
Hair dye has the universality that cutin protein fiber (especially human hair) dye of various original different colours is nature black,
Safe and coloring is quick.
We place the black hair sample after dyeing 6 months and 12 under the different temperatures of 0 DEG C to 50 DEG C of temperature
Month, the variation of color is not observed, for example fades etc.；Black hair after dyeing eluted repeatedly through clear water, 3 months and 6
It is compareed respectively within a month, color does not have significant change.Illustrate that the dyeing of these hair dyes is lasting, effect is good.
We have hair dyed at the white hair by the hair dye of embodiment 1-5 for each age level, it is found that coloring is quick
(5-10 minutes), effect good (natural black), safety (free from extraneous odour, non-stimulated) and coloring are persistently (6-12 a month non-discolouring).
These hair dyes are specifically for use in the hair quality of gook, especially Chinese, carry out white covering or white dye
It is black.The white hair in all ages and classes stages such as the children (young person with greying hair), young people, a middle-aged person and the elderly that bleach of selection hair into
Row Coloration experiment.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of compound for hair dyeing, which is characterized in that have the structural formula as shown in formula I or formula II：
Wherein, the X in formula II is Br or Cl.
2. a kind of preparation method of compound for hair dyeing, which is characterized in that include the following steps：
1) it is raw material with compound 1, in inert atmosphere, heating reflux reaction under the action of alkali carbonate is changed
Close object 2；
2) it is raw material with compound 2, in air or oxygen atmosphere, is stirred to react at room temperature, generates dimer compound 3；
3) it is raw material with compound 3, under inert atmosphere and stirring condition, Boron tribromide is added dropwise into raw material, during dropwise addition
Control system temperature is at -60 DEG C hereinafter, obtaining chemical combination shown in formula I in -40 DEG C or less reactions, demethylating protecting group after being added dropwise
Object；
Reaction route is as follows：
3. preparation method according to claim 2, which is characterized in that further include following steps：Compound shown in formula I is set
It in hydrogen bromide solution or hydrogen chloride solution, is stirred to react in the environment of 0 DEG C to room temperature, obtains compound shown in formula II, reacted
Process is as follows：
Wherein, the X in formula II is Br or Cl.
4. preparation method according to claim 2 or 3, which is characterized in that alkali carbonate and compound 1 in step 1)
Molar ratio be 2：1, the molar ratio of Boron tribromide and compound 3 is 5 in step 3)：1.
5. a kind of aerosol type one-pack type hair dye, which is characterized in that include melanin precursor, the melanin precursor is claim 1 institute
The compound stated.
6. aerosol type one-pack type hair dye according to claim 5, which is characterized in that the dosage of the melanin precursor be 0.5~
10wt%.
7. aerosol type one-pack type hair dye according to claim 6, which is characterized in that include following component：Melanin precursor 0.5~
10wt%, 2~12wt% of lipid, 2~5wt% of surfactant, 0.1~0.5wt% of antioxidant, 1~10wt% of alkaline agent,
0.1~1.0wt% of thickener, 1~10wt% of organic solvent, surplus are water.
8. aerosol type one-pack type hair dye according to claim 7, which is characterized in that the lipid refer to 1,3-BDO, glycerine,
The fatty alcohol of grape seed oil, rapeseed oil, castor oil, C12~18, the fatty alcohols of C16~18, cetylstearyl alcohol, palmitic acid
Isopropyl ester, isopropyl myristate, synthesis saualane, any one or two kinds or more in glycerin monostearate are answered
Match.
9. aerosol type one-pack type hair dye according to claim 7, which is characterized in that the alkaline agent refers to monoethanolamine, group ammonia
The compounding of acid, any one or two kinds or more in arginine.
10. aerosol type one-pack type hair dye according to claim 7, which is characterized in that the antioxidant refers to ascorbic acid, different
The compounding of any one or two kinds or more in ascorbic acid, sodium sulfite, the surfactant refers to cetostearyl alcohol
Any one in the stearic alcohol ether of polyether series, stearine, polyoxyethylene -2, the stearic alcohol ether of polyoxyethylene -21 or two
Kind or more compounding, the thickener refers to any one in hydroxyethyl cellulose, xanthans, chitosan, described organic
Solvent refers to 75% or more ethyl alcohol of concentration, ethylene glycol, glycerine, ethane, propane, butane, dimethyl ether or propylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810320906.XA CN108484471B (en) | 2018-04-11 | 2018-04-11 | Compound for dyeing hair and single-agent hair dye containing compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810320906.XA CN108484471B (en) | 2018-04-11 | 2018-04-11 | Compound for dyeing hair and single-agent hair dye containing compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108484471A true CN108484471A (en) | 2018-09-04 |
| CN108484471B CN108484471B (en) | 2021-04-13 |
Family
ID=63315476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810320906.XA Active CN108484471B (en) | 2018-04-11 | 2018-04-11 | Compound for dyeing hair and single-agent hair dye containing compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484471B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0356119A1 (en) * | 1988-08-26 | 1990-02-28 | Bristol-Myers Company | Skin tanning composition and method |
| JP2011046658A (en) * | 2009-08-27 | 2011-03-10 | Gekkeikan Sake Co Ltd | Melanin precursor-containing solution and method for producing the same |
| CN105496923A (en) * | 2015-12-21 | 2016-04-20 | 济南益豪环保技术有限公司 | Single-agent-type plant hair colorant |
| CN107540596A (en) * | 2017-07-27 | 2018-01-05 | 烟台六谛医药科技有限公司 | A kind of preparation method of the dihydroxy indole quinoline of compound 5,6 and its halogen acid salt |
-
2018
- 2018-04-11 CN CN201810320906.XA patent/CN108484471B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0356119A1 (en) * | 1988-08-26 | 1990-02-28 | Bristol-Myers Company | Skin tanning composition and method |
| JP2011046658A (en) * | 2009-08-27 | 2011-03-10 | Gekkeikan Sake Co Ltd | Melanin precursor-containing solution and method for producing the same |
| CN105496923A (en) * | 2015-12-21 | 2016-04-20 | 济南益豪环保技术有限公司 | Single-agent-type plant hair colorant |
| CN107540596A (en) * | 2017-07-27 | 2018-01-05 | 烟台六谛医药科技有限公司 | A kind of preparation method of the dihydroxy indole quinoline of compound 5,6 and its halogen acid salt |
Non-Patent Citations (2)
| Title |
|---|
| MAXIME ROCHE，等: "Tandem One-Pot Palladium-Catalyzed Coupling of Hydrazones,Haloindoles, and Amines: Synthesis of Amino‑N‑vinylindoles and Their Effect on Human Colon Carcinoma Cells", 《J. ORG. CHEM.》 * |
| S. N. MISHRA，等: "Studies Related to the Chemistry of Melanins. Part 1V.l Oxidation of 5,6- Dimethoxyindoline", 《J. CHEM. SOC. (C)》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108484471B (en) | 2021-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4997451A (en) | Oxidative hair dyeing compositions based on 4-aminophenol derivatives and new 4-aminophenol derivatives | |
| EP0962452B1 (en) | Oxidative hair dye compositions and methods containing 1-(4-aminophenyl)-2-pyrrolidinemethanols | |
| EP0891765B1 (en) | Oxidative hair dye compositions | |
| RU2060728C1 (en) | Agent for hair oxidative staining | |
| JPH11236323A (en) | New 3-aminopyrazlo(1, 5-a)pyrimidine, composition for dyeing keratinous fiber containing the same and dyeing by using the same | |
| US20020106341A1 (en) | Primary intermediates for oxidative coloration of hair | |
| US4092102A (en) | Dyeing keratin fibers with 2-substituted m-toluenediamines | |
| US3558259A (en) | Human hair dyeing with aminophenols | |
| JPWO2009041514A1 (en) | Dye for hair dyeing and composition for hair dyeing | |
| JPS6213462A (en) | Novel aminophenols and use thereof in oxidizing hair dye | |
| JPH04244011A (en) | Hair dyeing composition | |
| CA1100878A (en) | Methylenedioxy-benzene in oxydative dye | |
| AU716438B2 (en) | Aminophenol derivatives and their use in oxidation hair colorants | |
| JP3322971B2 (en) | Novel indoline compounds, dyeing compositions based on these compounds and methods for dyeing keratin fibers | |
| CA2253981C (en) | Novel bis-(2,4-diaminophenoxy) benzenes and their use as coupling components in oxidative hair coloring compositions and methods | |
| Zhang et al. | A new class of oxazolidinone-and phthalimide-based oxidation dye couplers and their effect on azomethine dye color | |
| CN108484471A (en) | A kind of aerosol type one-pack type hair dye for the compound of hair dyeing and comprising it | |
| JPS5967216A (en) | Hair dye | |
| AU2254500A (en) | Colouring agents with enzymes | |
| JPH07206649A (en) | Method of dyeing hair and its kit | |
| EP3616680A1 (en) | Compound containing basic dye and amino acid, hair dying dye, and hair dying composition | |
| GB1581377A (en) | Coloured cosmetic preparations | |
| JPH05503091A (en) | benzoxazine dye | |
| AU2001288261B2 (en) | Primary intermediates for oxidative coloration of hair | |
| KR102139150B1 (en) | Oxidation dye precursors and composition for dyeing comprising thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |