CN103554493B - Imidazolidine-type high-molecular spice precursor and synthesis thereof, purposes - Google Patents
Imidazolidine-type high-molecular spice precursor and synthesis thereof, purposes Download PDFInfo
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Abstract
The invention discloses a kind of imidazolidine-type high-molecular spice precursor and synthesis thereof, purposes; The present invention passes through aminated compounds
with described aldehydes or ketone fragrance molecule
reaction, synthesis imidazolidine intermediate
described imidazolidine intermediate and double methacrylate
carry out Michael addition polymerization, obtain described presoma
wherein, R1 and R2 is the residue deriving from aldehydes or ketone fragrance molecule, and R3 is hydrogen atom, alkyl or aromatic base, and R4 is hydrogen atom, alkyl or aromatic base, and R5 is hydrophilic radical.Imidazolidine-type high-molecular spice precursor suitable environment mild condition of the present invention, applied range, can use together with all alkalescence or neutral raw.
Description
Technical field
Synthesis that the present invention relates to spice precursor and uses thereof, is specifically related to a kind of imidazolidine-type high-molecular spice precursor and synthesis thereof, purposes.
Background technology
Aldehyde and ketone are very important spices, are often added to various product as shampoo, multifunctional cleaning agent, in the personal care such as washing powder or fabric softener or household cleaning products.In such applications, lasting fragrance is all needed.But, because the high volatile volatile that perfume molecules is intrinsic causes fragrance to rapidly disappear.In addition, aldehyde molecule is general all easily oxidized in atmosphere.
In order to address these problems, need to carry out chemical modification to them.Derivative after chemical modification is exactly so-called " spice precursor ".These spice precursor are designed to, accept outside stimulus as rayed, temperature variation, humidity change and the change of pH value time, original perfume molecules can be discharged.
Imidazolidine is unstable under acidic condition to be easily hydrolyzed, and discharges original aldehyde and ketone, and therefore, imidazolidine can be designed as spices inhibiter.The synthesis of imidazolidine is as follows:
imidazolidine is used as spice slow-releasing agent, and hydrolysis discharges original aldehyde and ketone in acid condition, as follows:
By finding the retrieval of existing document: WO2008/093272 (FIR-MENICHSA) discloses a series of acetal amine spice precursor, the structure be shown below:
spices aldehyde can be discharged after the hydrolysis of this acetal amine spice precursor.Aminal has five-ring (imidazolidine structure) and six-membered ring structure.But these spice precursor itself are low molecular, they some be also volatile, therefore can not be attached to material surface as fabric and skin surface.Although some lower molecular weight acetal amine spice precursor are not volatile, after discharging perfume molecules, owing to generating by product diamines odorous, can pollute or obscure the fragrance of required spices.WO00/02986 and US6790815R1 (P & G) discloses the adducts of branched polyethylenimine (BPEI) and fragrance aldehydes or ketones as spice precursor.In WO2009153209, BPEI is modified into has more hydrophilic derivatives, and then used as the macromolecular scaffold for fixing aldehyde and ketone, the spice precursor obtained is water miscible, and therefore they are easy to hydrolysis and discharge spices aldehyde and ketone.But utilize BPEI also to have shortcoming as the skeleton of macromolecular solid fixation material aldehyde and ketone, it comprises primary, secondary and tertiary three kinds of amidos, and primary amine can generate corresponding imines to aldehyde/reactive ketone, and secondary amine is the presoma of imidazolidine.Imidazolidine only just can generate with aldehyde/reactive ketone between adjacent two secondary amine, and such as, uncle-Bai-Bai-tertiary sequence can form corresponding imidazolidine to aldehyde/reactive ketone, but primary-uncle-Bai-tertiary sequence can not generate imidazolidine.Because the content of proper sequence depends on the production batch of BPEI, so using the skeleton of BPEI as fixing perfume molecules, carrying out production spice precursor can not have stable quality to ensure.
Therefore, be badly in need of a kind of easily synthesis of exploitation, there is the novel high polymer spice precursor of clear and definite imidazolidine structure.
Summary of the invention
The object of the invention is to overcome above-mentioned conventional perfumes presoma to produce and some spice precursor molecules of existing in application itself are lower molecular weights and volatile; Or although some spice precursor molecule is non-volatile, after discharging perfume molecules, remaining component is also volatile, and therefore its smell can pollute the fragrance of perfume molecules; Or the spice precursor of the polymer type of some branching is nonvolatile, after discharging perfume molecules, nubbin is also non-volatile, but due to branched polymer structure indefinite, the problems such as the difficult quality control of product, provide a kind of imidazolidine-type high-molecular spice precursor and synthesis thereof, purposes.The high-molecular spice precursor that main chain of the present invention has an imidazolidine group can be used in articles for washing, home care, personal-care supplies and some other need the Application Areas of long-term permanent fragrant.
The object of the invention is to be achieved through the following technical solutions:
First aspect, the present invention relates to a kind of imidazolidine-type high-molecular spice precursor, and its structural formula is such as formula shown in (I):
(I)，
Wherein, R1 and R2 is the residue deriving from aldehydes or ketone fragrance molecule, and R3 is hydrogen atom, alkyl or aromatic base, and R4 is hydrogen atom, alkyl or aromatic base, and R5 is hydrophilic radical.By selecting R5 group, the performance of polymer fragrance presoma can regulable control; Described aldehydes or ketone fragrance molecule are the aldehydes or the ketone that are conventionally used as spices; R3 and R4 is the residue of one of raw material deriving from imidazolidine type polymer fragrance presoma-imidazolidine, can be hydrogen atom, alkyl or aromatic group.
Preferably, described aldehyde perfume molecule is aubepine, geranial, citral, piperonylaldehyde, phenylacrolein, Vanillin, 10-undecylene aldehyde, enanthaldehyde, dimethyl-3-cyclohexene-1-formaldehyde, n-octaldehyde, dodecanal, α-methyl-p-tert.-butyl phenylpropionaldehyde or dihydro cinnamon aldehyde; Described ketone fragrance molecule is methyl phenyl ketone, piperitone, muskone, exaltone, 4-methyl acetophenone, alpha, beta-lonone, may blossom ketone, tonalide ketone, α-trans-Damascenone, 2-amyl group cyclopentanone, apione or δ-trans-Damascenone.By combining these aldehyde and ketone, the polymer-type spice precursor being combined with two or more perfume molecules can be synthesized.
Preferably, described R5 is ether, ester group, amide group, carbonate group, carboxyl, sulfuryl, sulfoxide group, alkylsulfonyl or phosphate.
Preferably, described R5 is ether, ester group, amide group or carboxyl.
Preferably, described R5 is ether, and its structural formula is such as formula shown in (II):
(II), wherein, r is arbitrary integer in 0 ~ 20, and s is arbitrary integer in 1 ~ 100.
More preferably, r is arbitrary integer in 0 ~ 5, and s is arbitrary integer in 1 ~ 50.
Most preferably, r is arbitrary integer in 0 ~ 5, and s is arbitrary integer in 1 ~ 20.
Second aspect, the present invention relates to a kind of synthetic method of aforesaid imidazolidine-type high-molecular spice precursor, comprises the steps:
A, aminated compounds
with described aldehydes or ketone fragrance molecule
reaction, synthesis imidazolidine intermediate
wherein, R1 and R2 is the residue deriving from aldehydes or ketone fragrance molecule, and R3 is hydrogen atom, alkyl or aromatic base, and R4 is hydrogen atom, alkyl or aromatic base;
B, described imidazolidine intermediate (namely there is the diamines of imidazolidine group) and double methacrylate
carry out Michael addition polymerization, obtain described imidazolidine-type high-molecular spice precursor; Described R5 is hydrophilic radical.
The third aspect, the present invention relates to a kind of purposes of aforesaid imidazolidine-type high-molecular spice precursor, and described imidazolidine-type high-molecular spice precursor can use together with alkalescence or neutral raw.
Preferably, described imidazolidine-type high-molecular spice precursor can mix together with shampoo, multifuctional cleaning agent, laundry detergent, fabric softener, reodorant, tensio-active agent, washing assistant, anti-dirt deposition agent, static inhibitor, spices, enzyme, whitening agent, SYNTHETIC OPTICAL WHITNER or filler.
The building-up process of imidazolidine-type high-molecular spice precursor of the present invention is a polyaddition.Imidazolidine diamines and double methacrylate, through Michael addition polyreaction, can obtain the phase emergencing copolymer that main chain has imidazolidine group; Be shown below:
Its mechanism of action is: under the pH condition of environment, and the imidazolidine group in main chain hydrolysis occurs and reaches the object of Co ntrolled release spices aldehyde/ketone molecule.Polymkeric substance relic after hydrolysis is nontoxic and not volatile; Hydrolytic process is shown below:
Compared with prior art, the present invention has following beneficial effect:
(1) high-molecular spice precursor applied range of the present invention: can use together with all alkalescence or neutral raw; Preferably mix together with shampoo, multifuctional cleaning agent, laundry detergent, fabric softener, reodorant, tensio-active agent, washing assistant, anti-dirt deposition agent, static inhibitor, spices, enzyme, whitening agent, SYNTHETIC OPTICAL WHITNER or filler.
(2) high-molecular spice precursor suitable environment mild condition of the present invention: can be used for temperature 0 ~ 80 DEG C, under drying conditions, under the condition of any pressure and pH value 7 ~ 13; More preferably, it can be used for temperature is 0 ~ 50 DEG C, and humidity is less than 70%, 1 ~ 2 normal atmosphere, and pH value is 7 ~ 10; Most preferably, they can be used in temperature is 20 ~ 60 DEG C, and humidity is less than 50%, 1 normal atmosphere, and pH value is 7 ~ 9.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is imidazolidine diamines 1 at deuterated methanol and imidazolidine-type high-molecular spice precursor polymkeric substance 3A in deuterated DMSO
13cNMR spectrogram;
Fig. 2 is under room temperature condition, and the time-dependent manner of imidazolidine-type high-molecular spice precursor polymkeric substance 3A, 3B octanal release behavior in water compares schematic diagram;
Fig. 3 is that the fragrance of imidazolidine-type high-molecular spice precursor polymkeric substance 3A is smelt and measured intention; Wherein, (a) is that the fragrance in the buffered soln of pH=3 is smelt and measured intention, and (b) is that the fragrance in the buffered soln of pH=5 is smelt and measured intention, and (c) is that the fragrance in water is smelt and measured intention.
Embodiment
Below in conjunction with specific embodiments and the drawings, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
Particularly, the aminated compounds in embodiments of the invention
adopt quadrol (R3=H, R4=H) representatively, but substituent R 3, R4 can be adopted to be the ethylene diamine derivative of alkyl or aromatic base as distortion of the present invention.
Aldoketones spices in the present invention adopts octanal as representative examples, but other can be adopted to can be used as the Carbonyl compounds (aubepine of spices as distortion of the present invention, geranial, citral, piperonylaldehyde, phenylacrolein, Vanillin, 10-undecylene aldehyde, enanthaldehyde, dimethyl-3-cyclohexene-1-formaldehyde, dodecanal, α-methyl-p-tert.-butyl phenylpropionaldehyde, dihydro cinnamon aldehyde, methyl phenyl ketone, piperitone, muskone, exaltone, 4-methyl acetophenone, alpha, beta-lonone, may blossom ketone, tonalide ketone, α-trans-Damascenone, 2-amyl group cyclopentanone, apione,-trans-Damascenone) in any one, because they all can with aminated compounds, particularly, corresponding imidazolidine diamines is generated by condensation dehydration reaction to the quadrol represented as it.
Hydrophilic group R5 in double methacrylate in the present invention is-(CH as representative examples
2cH
2o)
4-and-(CH
2cH
2o)
3-two kinds, but any distortion meeting described structural formula can be adopted as distortion of the present invention.Corresponding double methacrylate all can carry out Michael addition polyreaction to imidazolidine diamines and form the polymer fragrance presoma that corresponding main chain has imidazolidine group.Wherein
r is less and s is larger, and the wetting ability of the phase emergencing copolymer obtained is larger, is more easily hydrolyzed under mildly acidic conditions and discharges spices aldehyde/ketone, and namely fragrance release can be stronger.R is larger and s is larger, and the wetting ability of the phase emergencing copolymer obtained is less, and be more not easy hydrolysis under mildly acidic conditions and discharge spices aldehyde/ketone, namely fragrance release can be more weak.Therefore, more preferably, r is arbitrary integer in 0 ~ 5, and s is arbitrary integer in 1 ~ 50.Most preferably, r is arbitrary integer in 0 ~ 5, and s is arbitrary integer in 1 ~ 20.
embodiment
The synthesis of 1.1 imidazolidine-type high-molecular spice precursor
The synthesis of the imidazolidine-type high-molecular spice precursor of the present embodiment specifically comprises the steps:
The synthesis of (a) imidazolidine intermediate 1; Be shown below:
Octanal (2.56g, 50mmol, 1eq) is dripped in quadrol (1.20g, 50mmol).Room temperature reaction, after 1 hour, to reaction mixture normal hexane recrystallization, obtains product 1 for white powder (yield: 1.62g, 43%).
Confirm that product is 1 through nmr analysis, the chemical shift deriving from feature 1H-NMR and the 13C-NMR of the methyne (CH) of aldehyde radical is respectively 3.75ppm and 80.6ppm.
B () imidazolidine 1 and double methacrylate 2A or 2B synthesize through Michael's polyaddition polymkeric substance 3A or 3B that main chain contains imidazolidine group respectively; Be shown below:
Imidazolidine diamines 1 (341mg, 2.00mmol) with Viscoat 335HP 2A (604mg, 2.00mmol) or tri (propylene glycol) diacrylate 2B (600mg, 2.00mmol) in 1mL chloroform, under 40 DEG C of conditions react 48 hours.The transformation efficiency that 1HNMR tests acrylate is 96%.Gained reaction mixture normal hexane is precipitated, obtains corresponding polymkeric substance 3A (yield: 676mg, 72.0%; M
n=1800, M
w/ M
n=1.47) (13C-NMR spectrogram is shown in Fig. 1) or polymkeric substance 3B (yield: 517mg, 55.0%; M
n=1600, M
w/ M
n=1.31).The octanal amount be incorporated in polymkeric substance is 27.0% (weight).3A and 3B is all water insoluble, and they form milk sap (as shown in table 1) in water.
Table 1. is from the indices of imidazolidine diamines 1 and diacrylate 2 Reactive Synthesis polymkeric substance 3
The soluble test of 1.2 imidazolidine-type high-molecular spice precursor
In order to investigate the water-soluble of imidazolidine-type high-molecular spice precursor polymkeric substance 3A and 3B, adopt the visible-transmittance (as shown in table 2) of both ultraviolet spectrophotometer mensuration at wavelength 500nm place;
The dissolving situation of table 2. polymkeric substance 3 in water
The hydrolysis experiment of 1.3 imidazolidine-type high-molecular spice precursor
Imidazolidine-type high-molecular spice precursor polymkeric substance 3A or 3B is added in 5 ml waters, and be at room temperature hydrolyzed test.With the concentration of octanal for 10.0mM extrapolates the concentration of 3A or 3B.In order to the octanal quantizing to discharge in hydrolytic process with GC, in solution, add 5 ml n-hexanes and 10 milligrams of dodecanes (interior mark).After stirring for some time, get about 0.1 ml sample from normal hexane layer, and analyze with GC.Their conduct hydrolysis in water as shown in Figure 2, in figure [3A]
0=4.70g/L, [3B]
0=4.70g/L ([octanal]
0=10.0mM); As shown in Figure 2, these two kinds of polymkeric substance all can discharge octanal gradually, and tend towards stability after 24h.This may be because the polymkeric substance of partial hydrolysis forms micella in water, and therefore, shipwreck, to enter the core of imidazolidine group hydrophobic in micella, is hydrolyzed further to make them.But they still have the potentiality as spice precursor.Because the situation in actual applications, forming micella seldom exists.Therefore, they are potential Pro-perfumes, because the pH value of water is similar to the pH of surrounding environment atmosphere.
Although in hydrolysising experiment, imidazolidine-type high-molecular spice precursor polymkeric substance 3A and 3B contains the octanal of identical amount, and the octanal rate of release of 3A is faster than 3B, and this holds the wetting ability higher than 3B owing to 3A.
The test of smelling of 1.4 imidazolidine-type high-molecular spice precursor is tested
Imidazolidine-type high-molecular spice precursor polymkeric substance 3A is dissolved in acetone, and based on octanal, the concentration of polymkeric substance is 0.3M.As a reference, the acetone soln of the pure octanal of 0.3M is prepared.Smell test specimens sliver 6 and soak two centimetres in detected solution, i.e. in the acetone soln of 3A and pure octanal, then drying at room temperature.Every day use water, pH=3 and pH=5 buffered soln carry out spraying and carry out fragrance and smell survey.The intensity of the fragrance after sprinkling is assessed as 0 to 6 points.The undesirable strong fragrance of flavour intensity index definition: 6=; 5=is very strong; 4=is strong; 3=is stronger; 2=is happy; 1=can smell; 0=smell less than.Smell test result as shown in Figure 3, as shown in Figure 3, the performance of imidazolidine-type high-molecular spice precursor polymkeric substance 3A is more effective, and it provides a lasting fragrance releasing effect than pure octanal.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. an imidazolidine-type high-molecular spice precursor, its structural formula is as shown in formula I:
Wherein, R1 and R2 is the residue deriving from aldehydes or ketone fragrance molecule, and R3 is hydrogen atom, alkyl or aromatic base, and R4 is hydrogen atom, alkyl or aromatic base, and R5 is hydrophilic radical.
2. imidazolidine-type high-molecular spice precursor as claimed in claim 1, it is characterized in that, described aldehyde perfume molecule is aubepine, geranial, citral, piperonylaldehyde, phenylacrolein, Vanillin, 10-undecylene aldehyde, enanthaldehyde, dimethyl-3-cyclohexene-1-formaldehyde, n-octaldehyde, dodecanal, α-methyl-p-tert.-butyl phenylpropionaldehyde or dihydro cinnamon aldehyde; Described ketone fragrance molecule is methyl phenyl ketone, piperitone, muskone, exaltone, 4-methyl acetophenone, alpha, beta-lonone, may blossom ketone, tonalide ketone, α-trans-Damascenone, 2-amyl group cyclopentanone, apione or δ-trans-Damascenone.
3. imidazolidine-type high-molecular spice precursor as claimed in claim 1, it is characterized in that, described R5 is ether, amide group, carboxyl, alkylsulfonyl or phosphate.
4. imidazolidine-type high-molecular spice precursor as claimed in claim 3, it is characterized in that, described R5 is ether, amide group or carboxyl.
5. imidazolidine-type high-molecular spice precursor as claimed in claim 3, it is characterized in that, described R5 is ether, and its structural formula is as shown in formula II:
wherein, r is arbitrary integer in 0 ~ 20, and s is arbitrary integer in 1 ~ 100.
6. imidazolidine-type high-molecular spice precursor as claimed in claim 5, it is characterized in that, r is arbitrary integer in 0 ~ 5, and s is arbitrary integer in 1 ~ 50.
7. imidazolidine-type high-molecular spice precursor as claimed in claim 6, it is characterized in that, r is arbitrary integer in 0 ~ 5, and s is arbitrary integer in 1 ~ 20.
8. a synthetic method for the imidazolidine-type high-molecular spice precursor according to any one of claim 1 ~ 7, is characterized in that, comprises the steps:
A, aminated compounds
with described aldehydes or ketone fragrance molecule
reaction, synthesis imidazolidine intermediate
wherein, R1 and R2 is the residue deriving from aldehydes or ketone fragrance molecule, and R3 is hydrogen atom, alkyl or aromatic base, and R4 is hydrogen atom, alkyl or aromatic base;
B, described imidazolidine intermediate and double methacrylate
carry out Michael addition polymerization, obtain described imidazolidine-type high-molecular spice precursor; Described R5 is hydrophilic radical.
9. a purposes for the imidazolidine-type high-molecular spice precursor according to any one of claim 1 ~ 7, is characterized in that, described imidazolidine-type high-molecular spice precursor can use together with alkalescence or neutral raw.
10. the purposes of imidazolidine-type high-molecular spice precursor according to claim 9, it is characterized in that, described imidazolidine-type high-molecular spice precursor can mix together with shampoo, multifuctional cleaning agent, laundry detergent, fabric softener, reodorant, tensio-active agent, washing assistant, anti-dirt deposition agent, static inhibitor, spices, enzyme, whitening agent, SYNTHETIC OPTICAL WHITNER or filler.
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| CN1789399A (en) * | 1998-07-10 | 2006-06-21 | 宝洁公司 | Soft compound and use thereof |
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| CN1789399A (en) * | 1998-07-10 | 2006-06-21 | 宝洁公司 | Soft compound and use thereof |
| CN101605765A (en) * | 2007-01-30 | 2009-12-16 | 弗门尼舍有限公司 | Active aldehydes and the ketone controlled release from the equilibrated dynamic mixtures |
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