CN105884620A - 4-Hydroxyl-1,3 di-phthalate derivatives and preparation and application thereof - Google Patents
4-Hydroxyl-1,3 di-phthalate derivatives and preparation and application thereof Download PDFInfo
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- CN105884620A CN105884620A CN201610257971.3A CN201610257971A CN105884620A CN 105884620 A CN105884620 A CN 105884620A CN 201610257971 A CN201610257971 A CN 201610257971A CN 105884620 A CN105884620 A CN 105884620A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0061—Essential oils; Perfumes compounds containing a six-membered aromatic ring not condensed with another ring
Abstract
The invention relates to 4-hydroxyl-1,3 di-phthalate derivative and preparation and application thereof. A compound is obtained by subjecting 4-hydroxyl-1,3 phthalic acid to esterification with various fatty alcohols or aromatic alcohols. The derivative has a structural general formula (I) shown below, wherein R is selected from C1-C12 alkyls, C3-C12 naphthenic groups, substituted or non-substituted C6 acryl, substituted or non-substituted C6 heterocyclic aryl or substituted or non-substituted C3-C12 heterocyclic aryls; the substituted group is selected from C1-C12 alkyls, halogen, nitro groups, cyano groups or amino groups; heteroatoms in the heterocyclic aryls and heterocyclic alkyls are selected from N, O or S. The derivative has high ultraviolet absorptivity and certain aroma and is expected to be applied in cosmetic field, medicine field, pesticide field, polymer material field and the other fields. A preparation process of the derivative is simple and short, materials are rich in origin and low in rice, 4-hydroxyl-1,3 phthalic acid is byproduct waste from industrial production of salicylic acid, and the derivative has good economic benefit and promising application prospect.
Description
Technical field
The invention belongs to Field of Fine Chemicals, relate to a kind of 4-hydroxyl-1,3 ester analog derivatives
Preparation and application.
Background technology
Salicylate is the fine chemical product that a class is important, is mainly used for as medicine and the intermediate of pesticide, perfume (or spice)
Material and UV absorbent.
Salicylate is to apply a class UV absorbent the earliest.For many years, substantial amounts of salicylic acid ultra-violet absorption
Agent is produced, and is once widely used, such as phenyl salicylate, benzyl salicylate, amyl salicylate, bigcatkin willow
Hydrochlorate (potassium, sodium, triethanolamine), ethylhexyl salicylate, salicylic acid isooctyl ester, salicylic acid p-tert-butyl group phenyl ester (TBS),
Double acid double phenol A ester (BAD) etc..This kind of UV absorbent to the ability of ultra-violet absorption when starting very
Low, but after ultraviolet irradiates certain time, its absorption is gradually increased, until absorption maximum.This be due to its
Ultraviolet irradiates and issues raw molecular rearrangement, defines the benzophenone structural that ultraviolet absorption ability is strong, thus strengthens it
Ultra-violet absorption effect.Salicylic acid UV absorbent is the gentleest, stable, has preferable safety,
Particularly the safest to skin, and in product system, compatibility is good.Oil-soluble salicylic acid esters, be
The good solubilizing agent of some sunscreen raw materials, such as ethylhexyl salicylate, can increase crystalline state oil-soluble UV line
The dissolubility of absorbent benzophenone, so that sun-proof efficiency improves.Water miscible salicylic acid salt is for skin
Affinity is relatively good, has the effect of enhancing to SPF (sun protection factor) SPF of sunscreen products, and may be used for hair-care articles
In sun-proof.China's " cosmetics health specification " (2002 editions) regulation can use 3 kinds of salicylic acid UV absorbent.
Fragrance same clan spice occupies considerable status in synthetic spice, as benzylalcohol, phenethanol, vanillin,
Eugenol, benzyl acetate, essence of Niobe, methyl salicylate, isoamyl salicylate, salicylic acid cyclohexyl, water
Poplar acid benzyl esters etc., they are important fragrance components, have considerable amount of production and use every year.
Methyl salicylate has another name called wintergreen oil, has the abnormal smells from the patient of the strongest similar Herba pyrolae japonicae, is commonly used in pharmaceutical preparation
Oral cavity medicine and varnish etc. from pastil, be also used in chewing gum, collutory, toothpaste type product, at wind oil
The medicines such as essence, menthocamphorate, safflower oil also there is extensive application.Methyl salicylate or a kind of important organic
Centre is stopped, in order to synthesize medicine, insecticide, antibacterial, spice, fiber dyeing auxiliaries etc..
Ethyl salicylate has the special aromatic odor being similar to Ilicis Purpureae, can be used for preparing floral type spice.Fragrant at mouth
Also having application in the products such as sugar, essential balm, consumption is few compared with methyl salicylate.Ethyl salicylate also can be used simultaneously
Make solvent or for organic synthesis.
Isoamyl salicylate is one of most important product in pentyl ester, has the most lasting medicinal herbs fragrance and Fructus Fragariae Ananssae
Sour-sweet fragrance, be to be in harmonious proportion the host of the essence such as three leaf oils.It is used as blender in the essence such as modulation Dianthus carryophyllus
And fixastive, it is the edible essence of GB GB2760-86 permission use.
Benzyl salicylate has faint fragrant and sweet abnormal smells from the patient, can be as the solvent of nitro musk, synthetic musk, the fragrance of a flower
The fixastive of essence is it can also be used to eat in fruit essence.Additionally, benzyl salicylate is alternatively arranged as sterilization and anticorrosion
Agent, makees UV absorbent etc. in sun-proofization shape product.
4-hydroxyl-1,3 phthalic acids are the main components of salicylic acid commercial production sublimation purification operation toffee residue.This
A little brown residue, including 80～4-hydroxyl-1 of 83%, 3 phthalic acids, 2～2-hydroxyl-1 of 3%, 3 benzene diformazans
Acid, 10～12% salicylic acid distilled the most completely and the inorganic material of 24%, be considered as a kind of work the most always
Industry refuse.China is salicylic acid big producing country, and annual production, more than 50,000 tons, utilizes Kolbe-Schmitt reaction industry
Salicylic acid is prepared in change can produce the 4-hydroxyl of 3～5%--1,3 phthalic acid by-product, there is thousands of tons of 4-hydroxyl the most every year
-1,3 phthalic acids may utilize.To 4-hydroxyl-1,3 phthalic acids are furtherd investigate and are developed, and can produce considerable
Social benefit and economic benefit.
Producing by-product 4-hydroxyl-1 about salicylic acid at present, the research application report of 3 phthalic acids is considerably less.From
Seeing in structure, 4-hydroxyl-1,3 phthalic acids are than salicylic acid the most carboxyls in hydroxyl para-position.Salicylate
Series products is typically esterified in the presence of the catalyst such as sulphuric acid with salicylic acid and hydroxy compounds and obtains, or utilizes ester exchange
Method prepares, it is possible to reacted generation by bigcatkin willow acyl chlorides and alcohols.Use similar preparation method, by 4-hydroxyl-1,3 benzene two
Formic acid carries out esterification with various fatty alcohol or aromatic alcohol, can obtain corresponding 4-hydroxyl-1,3 ester classes
Derivant.Experiment shows, these 4-hydroxyl-1, and 3 ester analog derivatives mostly have stronger ultraviolet
Absorbent properties, and have certain fragrance, it is worth research and development further, is expected in cosmetics, medicine, agriculture
The numerous areas such as medicine, polymeric material obtains application.
Summary of the invention
Technical problem: it is an object of the invention to provide a kind of 4-hydroxyl-1, the system of 3 ester analog derivatives
Preparation Method and application.It is brief that the method has preparation technology, the feature that abundant raw material source is cheap.
Technical scheme: a kind of 4-hydroxyl-1 of the present invention, the structure such as formula of 3 ester analog derivatives
(I) shown in:
In formula (I): R is selected from C1-C12Alkyl, C3-C12Cycloalkyl, replacement or unsubstituted C6Aryl, take
Generation or unsubstituted C6Heteroaryl or replacement or unsubstituted C3-C12Heterocyclylalkyl；Described substituent group is selected from:
C1-C12Alkyl, halogen, nitro, cyano group or amino；Hetero atom choosing in described heteroaryl and Heterocyclylalkyl
From: N, O or S.
In logical formula (I), R is selected from C1-C8Alkyl, replacement or unsubstituted C6Aryl, phenyl C1-C8Alkyl.
In logical formula (I), R is selected from isopropyl, isobutyl group, isopentyl, iso-octyl, phenyl, benzyl or p-
Tert-butyl-phenyl.
Described 4-hydroxyl-1,3 ester analog derivatives comprise following compound:
4-hydroxyl-1,3 dimethyl phthalate；4-hydroxyl-1,3 diethyl phthalates；4-hydroxyl-1,3 benzene diformazans
Acid dipropyl；4-hydroxyl-1,3 phthalic acid diisopropyl esters；4-hydroxyl-1,3 phthalic acid dibutyl esters；4-hydroxyl
-1,3 phthalic acid diisobutyl esters；4-hydroxyl-1,3 phthalic acid diamyl esters；4-hydroxyl-1,3 phthalic acid diisoamyls
Ester；4-hydroxyl-1,3 phthalic acid dihexyls；4-hydroxyl-1,3 phthalic acid two dissident's esters；4-hydroxyl-1,3 benzene two
Formic acid two heptyl ester；4-hydroxyl-1,3 phthalic acid two isocyanates；4-hydroxyl-1,3 dioctyl phthalates；4-hydroxyl
-1,3 phthalic acid di-isooctyls；4-hydroxyl-1,3 phthalic acid diphenyl esters；4-hydroxyl-1,3 phthalic acid dibenzyls
Ester；4-hydroxyl-1,3 phthalic acids are to chlorobenzene ester；4-hydroxyl-1,3 phthalic acids two are to tert-butyl group phenyl ester；4-
Hydroxyl-1,3 phthalic acid bicyclo-pentyl esters；4-hydroxyl-1,3 dicyclo-hexyl phthlates.
This derivant is applied to UV absorbent, uvioresistant stabilizer or the preparation of synthetic spice；Make
It is applied to preparation medicine and pesticide for intermediate.
Described 4-hydroxyl-1, the preparation method of 3 ester analog derivatives is:
1., with raw material alcohol roh as solvent, dissolve 4-hydroxyl-1,3 phthalic acids, under ice bath, drip SOCl2, instead
Answer temperature rising reflux after 1h, react complete evaporated under reduced pressure, add ethyl acetate, with saturated sodium bicarbonate solution,
Saturated aqueous common salt washs, and drying, is evaporated to obtain crude product, after recrystallization white solid target compound 4-hydroxyl
-1,3 ester analog derivatives.
2., with raw material alcohol roh and DMF as solvent, dissolve 4-hydroxyl-1,3 phthalic acids, add catalyst
NaHSO4, backflow, react complete and be extracted with ethyl acetate, saturated sodium bicarbonate solution, saturated common salt are washed
Washing, drying, decompression except the raw alcohol of residual, obtains light yellow liquid targeted except solvent, crude product decompression distillation
Compound 4-hydroxyl-1,3 ester analog derivatives.
3. dissolving in DMF by 4-hydroxyl-isophathalic acid, ice-water bath is dividedly in some parts sodium hydride, and stirring is to no longer there being gas to produce
Raw, drip halogenated aryl hydrocarbon or halogenated hydrocarbons RX under room temperature, after reaction 1h, temperature rising reflux terminates to reaction；Reactant liquor cools down
In falling back, extracting with ether, saturated common salt is washed, drying, and decompression is except solvent afforded crude material, recrystallization
After white solid target compound 4-hydroxyl-1,3 ester analog derivatives.
Wherein RX refers to that halogenated aryl hydrocarbon or the halogenated hydrocarbons RX of the preceding paragraph, X are halogen.
4. with raw material alcohol roh as solvent, adding 4-hydroxyl-1,3 dimethyl phthalate and Feldalat NM, stirring adds
Steam the methanol of generation while heat, react in the reactant liquor water of falling people after terminating, be layered, take off a layer oily
Thing. with 20% acetum washing. then washing with water to neutrality, anhydrous magnesium sulfate is dried, and liquid is distilled to obtain in decompression
Target compound 4-hydroxyl-1,3 ester analog derivatives.
Beneficial effect: material 4-hydroxyl-1 disclosed by the invention, 3 ester analog derivative novel structures,
There is stronger uv absorption property and certain fragrance, be expected at cosmetics, medicine, pesticide, polymeric material
The numerous areas such as material obtain application.Preparation technology of the present invention is brief, and abundant raw material source is cheap, wherein 4-hydroxyl
-1,3 phthalic acids are salicylic acid commercial production waste by-product, have preferable economic benefit and application prospect.
Detailed description of the invention
Described 4-hydroxyl-1, the preparation method of 3 ester analog derivatives is one of following methods:
The logical method of synthesis, 1. with raw material alcohol roh as solvent, is dissolved 4-hydroxyl-1,3 phthalic acids, is dripped under ice bath
SOCl2, temperature rising reflux after reaction 1h, reacts complete evaporated under reduced pressure, adds appropriate ethyl acetate, use saturated carbon
Acid hydrogen sodium solution, saturated aqueous common salt washing, drying, be evaporated to obtain crude product, after recrystallization white solid target
Compound.Yield: 85～95%.
2. the logical method of synthesis with raw material alcohol roh and DMF as solvent, is dissolved 4-hydroxyl-1,3 phthalic acids, is added and urge
Agent NaHSO4, backflow, react complete and be extracted with ethyl acetate, saturated sodium bicarbonate solution, saturated common salt
Water washs, drying, and decompression except the raw alcohol of residual, obtains light yellow with oil pump decompression distillation except solvent, crude product
Liquid target compound, yield: 80～90%.
The logical method of synthesis is 3. by 4-hydroxyl-1, and 3 phthalic acids dissolve in DMF, and ice-water bath is dividedly in some parts sodium hydride, stirring
To no longer there being gas to produce, dripping halogenated aryl hydrocarbon or halogenated hydrocarbons RX under room temperature, after reaction 1h, temperature rising reflux is to reacting knot
Bundle.During reactant liquor cooling is fallen back, extracting with ether, saturated common salt is washed, drying, and decompression obtains except solvent
Crude product, obtains white solid target compound, yield: 60～70% after recrystallization.Wherein X is halogen.
The logical method of synthesis, 4. with raw material alcohol roh as solvent, adds 4-hydroxyl-1,3 dimethyl phthalate and methanol
Sodium, agitating heating, steam the methanol of generation while reaction, react in the reactant liquor water of falling people after terminating, divide
Layer, takes layer oily matter, with 20% acetum washing, then washes with water to neutrality, and anhydrous magnesium sulfate is dried
Oily liquids target compound is distilled to obtain in decompression, yield: 80～90%.
The invention still further relates to containing aforementioned 4-hydroxyl-1, the ultraviolet absorber of 3 ester analog derivatives, people
Work synthetic perfume, medicine and pesticide.
Aforesaid 4-hydroxyl-1,3 ester analog derivatives can be used for preparing uvioresistant stabilizer, people
In work synthetic perfume, medicine and pesticide.
Embodiment of the present invention describes the preparation method of each compound in general structure (I) in detail, by reality
Execute example and further illustrate the present invention, but present disclosure can not be limited:
Embodiment 1:4-hydroxyl-1, the preparation of 3 diethyl phthalates
In 50ml there-necked flask, add 30ml ethanol, add 1.82g (0.01mol) 4-hydroxyl-1,3 benzene
Dioctyl phthalate, drips 1.5ml (0.02mol, 2.38g) SOCl under ice bath2, drip complete continuation and react liter after 1h
Temperature backflow, TLC follows the trail of to the disappearance of raw material point.Reactant liquor is concentrated after doing, add appropriate ethyl acetate, organic
The most successively with saturated sodium bicarbonate solution, saturated aqueous common salt washing, anhydrous sodium sulfate is dried.Evaporated under reduced pressure filtrate,
Add 10ml ethanol to be dissolved by residue, be placed in refrigerator overnight, have White snowflake shape solid to separate out, filter,
Filter cake distilled water wash, oven drying at low temperature sample, obtain 2.26g product, yield 95.0%.Mp:54～55 DEG C,
1H NMR(CDCl3；δ ppm): 1.37-1.62 (td, 6H, CH3), 4.33-4.40 (q, 2H, CH2), 4.41-4.48 (q,
2H, CH2), 6.98-7.01 (d, 1H, Ar), 8.09-8.12 (dd, 1H, Ar), 8.55-8.56 (d, 1H, Ar),
11.29 (s, 1H, OH).
Embodiment 2:4-hydroxyl-1, the preparation of 3 phthalic acid dipropyls
In 50ml there-necked flask, add 30ml normal propyl alcohol, add 1.82g (0.01mol) 4-hydroxyl--1,3
Phthalic acid, drips 1.5ml (0.02mol, 2.38g) SOCl under ice bath2, after dripping complete continuation reaction 1h
Temperature rising reflux, TLC follows the trail of to the disappearance of raw material point.By reactant liquor evaporated under reduced pressure, add acetic acid ethyl dissolution remaining
Thing, successively with saturated sodium bicarbonate solution, saturated aqueous common salt washing, anhydrous sodium sulfate is dried.Concentrating under reduced pressure is filtered
Liquid, is placed in refrigerator overnight, has white powdery solids to separate out, and filters, naturally dries, and obtains 2.51g and produces
Thing, yield 94.3%.Mp:23～24 DEG C, 1H NMR (CDCl3；δ ppm): 1.01-1.08 (td, 6H, CH3),
1.76-1.88 (h, 4H, CH2), 4.25-4.37 (t, 4H, CH2), 6.99-7.02 (d, 1H, Ar), 8.10-8.13 (dd,
1H, Ar), 8.57 (d, 1H, Ar), 11.29 (s, 1H, OH).
Embodiment 3:4-hydroxyl-1, the preparation of 3 phthalic acid dibenzyl esters
By 1.82g (0.01mol) 4-hydroxyl-1,3 phthalic acids are dissolved in 70ml DMF, are dividedly in some parts under ice bath
0.48g (0.02mol) sodium hydride, stirring is to no longer there being gas to produce, then drips 2.4ml (0.02mol) cylite,
Temperature rising reflux after stirring reaction 1h under room temperature, TLC follows the trail of to the disappearance of raw material point.During reactant liquor cooling is fallen back,
Extracting with ether, saturated common salt is washed, and anhydrous sodium sulfate is dried, evaporated under reduced pressure filtrate, and residue uses column chromatography
(ethyl acetate: petroleum ether=5: 1) obtains 2.20g white solid, and productivity is 60.7%.Mp:68～70 DEG C, 1H
NMR(CDCl3；δ ppm): 5.36 (s, 2H, CH2), 5.42 (s, 2H, CH2), 7.00-7.03 (d, 1H, Ar),
7.26-7.45 (m, 10H, Ph), 8.14-8.18 (dd, 1H, Ar), 8.65-8.66 (d, 1H, Ar), 11.23 (s, 1H,
OH)。
Embodiment 4:4-hydroxyl-1, the preparation of 3 phthalic acid di-isooctyls
1.82g (0.01mol) 4-hydroxyl-1,3 phthalic acids, 0.26gNaHSO is added in 50ml there-necked flask4,
30ml isooctanol and 5mlDMF, stirring reaction at 150 DEG C, TLC follows the trail of to the disappearance of raw material point.By reactant liquor
Being extracted with ethyl acetate, then wash with saturated sodium bicarbonate solution, saturated aqueous common salt successively, anhydrous sodium sulfate is done
Dry, remove ethyl acetate under reduced pressure, residual solution decompression distillation, except excess isooctanol (90～92 DEG C/170Pa), obtains 3.66g
Light yellow liquid target compound.Yield: 89.5%.1H NMR(CDCl3；δ ppm): 5.36 (s, 2H, CH2),
5.42 (s, 2H, CH2), 7.00-7.03 (d, 1H, Ar), 7.26-7.45 (m, 10H, Ar)), 8.14-8.18 (dd,
1H, Ar), 8.65-8.66 (d, 1H, Ar), 11.23 (s, 1H, OH).
Embodiment 5:4-hydroxyl-1, the preparation of 3 dicyclo-hexyl phthlates
2.10g (0.01mol) 4-hydroxyl--1,3 dimethyl phthalate, 20ml is added in 50ml there-necked flask
Hexalin and 0.054g (0.001mol) Feldalat NM, heat under magnetic agitation, steam the methanol of generation simultaneously,
Reacting by the reactant water of falling people after terminating, layering takes layer oily matter. with 20% acetum washing. then
Being washed to neutrality, anhydrous magnesium sulfate is dried, and residual solution decompression distillation subtracts except excess Hexalin (75～78 DEG C/170Pa)
Pressure distills to obtain 2.98g oily liquids target compound.Yield: 85.5%.1H NMR(CDCl3；δ ppm):
1.30-1.96 (m, 20H, CH2), 3.89 (s, 2H, CH), 7.08-7.09 (d, 1H, Ar), 7.93-7.94 (d,
1H, Ar), 8.20 (s, 1H, Ar), 11.23 (s, 1H, OH).
Embodiment 6:4-hydroxyl-1, the preparation of 3 phthalic acid diphenyl esters
In 50ml there-necked flask, add 30ml dichloromethane, add 1.82g (0.01mol) 4-hydroxyl-1,3
Phthalic acid and 1.88g phenol (0.02mol), drip 1.5ml (0.02mol, 2.38g) SOCl under ice bath2,
Dripping complete continuation and react temperature rising reflux after 1h, TLC follows the trail of to the disappearance of raw material point.By reactant liquor evaporated under reduced pressure,
Add acetic acid ethyl dissolution residue, successively with saturated sodium bicarbonate solution, saturated aqueous common salt washing, anhydrous sulfur
Acid sodium is dried.Concentrating under reduced pressure filtrate, is placed in refrigerator overnight, has white powdery solids to separate out, and filters, from
So dry, obtain 2.87g product, yield 85.3%.1H NMR(CDCl3；δ ppm): 7.13-7.14 (d, 1H,
Ar), 7.32-7.40 (m, 6H, Ar), 7.48-7.52 (dd, 4H, Ar), 8.14-8.17 (d, 2H, Ar), 11.23 (s,
1H, OH).
Embodiment 7:4-hydroxyl-1, the preparation to tert-butyl group phenyl ester of 3 phthalic acids two
Addition 30ml DMF, 1.82g (0.01mol) 4-hydroxyl-1 in 50ml there-necked flask, 3 phthalic acids,
0.26gNaHSO4, 3.01g (0.02mol) p-t-butyl phenol, it is stirred at reflux reaction, TLC follows the trail of to raw material
Point disappears.Reactant liquor is extracted with ethyl acetate, more successively with saturated sodium bicarbonate solution, saturated common salt washing
Washing, anhydrous sodium sulfate is dried, and removes ethyl acetate under reduced pressure, obtains 3.67g target compound.Yield: 81.9%.
1H NMR(CDCl3；δ ppm): 1.28 (s, 18H, CH3), 6.96～6.99 (m, 4H, Ar), 7.16-7.18 (d,
1H, Ar), 7.40-7.43 (m, 4H, Ar)), 8.15-8.17 (dd, 1H, Ar), 8.47-8.48 (d, 1H, Ar),
11.23 (s, 1H, OH).
Embodiment 8:4-hydroxyl-1, the ultraviolet absorbability of 3 ester analog derivatives measures
Using ethanol as solvent, prepare 4-hydroxyl-1 that 6 concentration is 0.05mg/ml, 3 ester classes
Derivative solution, measures its uv absorption property, and the data obtained is depicted as following form.
The uv absorption property of table 1 target product
Embodiment 9:4-hydroxyl-1, the fragrance test of 3 ester analog derivatives
Due to 4-hydroxyl-1,3 ester analog derivatives and salicylic acid ester perfume have similar structural characteristics,
Present invention 4-hydroxyl-1 to having synthesized, the fragrance characteristic of 3 ester analog derivatives has carried out tentatively smelling
Survey.Experimental technique is to add in 50ml teacup respectively to add 20ml distilled water or ethanol in 5 dark brown cups,
Certain density 4-hydroxyl-1,3 ester analog derivative samples and benzyl salicylate reference substance add immediately
Wherein in two glasss, with distinguish fragrant paper dip container respectively in sample (both must be close to standard sample about 1～2cm
Equivalent), press from both sides on the tester rack with clip, then carry out commenting perfume (or spice) with olfactory sensation.Test sample is judged by commenting taste requirement
The most savory.
7 4-hydroxyl-1 of preliminary test of the present invention, 3 ester analog derivatives: 4-hydroxyl-1,3 benzene two
Formic acid dimethyl ester, 4-hydroxyl-1,3 diethyl phthalates, 4-hydroxyl-1,3 phthalic acid dipropyls, 4-hydroxyl
-1,3 phthalic acid dibenzyl esters, 4-hydroxyl-1,3 phthalic acid di-isooctyls, 4-hydroxyl-1,3 phthalic acid diphenyl esters
With 4-hydroxyl-1,3 dicyclo-hexyl phthlates, result shows these 4-hydroxyl-1, and 3 ester classes derive
Thing has certain fragrance.
Claims (10)
1. 4-hydroxyl-1,3 ester analog derivatives, it is characterised in that the structure of this derivant is as logical
Shown in formula (I):
In formula (I): R is selected from C1-C12Alkyl, C3-C12Cycloalkyl, replacement or unsubstituted C6Aryl, take
Generation or unsubstituted C6Heteroaryl or replacement or unsubstituted C3-C12Heterocyclylalkyl；Described substituent group is selected from:
C1-C12Alkyl, halogen, nitro, cyano group or amino；Hetero atom choosing in described heteroaryl and Heterocyclylalkyl
From: N, O or S.
4-hydroxyl-1 the most according to claim 1,3 ester analog derivatives, it is characterised in that:
In logical formula (I), R is selected from C1-C8Alkyl, replacement or unsubstituted C6Aryl, phenyl C1-C8Alkyl.
4-hydroxyl-1 the most according to claim 1,3 ester analog derivatives, it is characterised in that:
In logical formula (I), R is selected from isopropyl, isobutyl group, isopentyl, iso-octyl, phenyl, benzyl or p-tertiary fourth
Base phenyl.
4-hydroxyl-1 the most according to claim 1,3 ester analog derivatives, it is characterised in that institute
4-hydroxyl-1 stated, 3 ester analog derivatives comprise following compound:
4-hydroxyl-1,3 dimethyl phthalate；4-hydroxyl-1,3 diethyl phthalates；4-hydroxyl-1,3 benzene diformazans
Acid dipropyl；4-hydroxyl-1,3 phthalic acid diisopropyl esters；4-hydroxyl-1,3 phthalic acid dibutyl esters；4-hydroxyl
-1,3 phthalic acid diisobutyl esters；4-hydroxyl-1,3 phthalic acid diamyl esters；4-hydroxyl-1,3 phthalic acid diisoamyls
Ester；4-hydroxyl-1,3 phthalic acid dihexyls；4-hydroxyl-1,3 phthalic acid two dissident's esters；4-hydroxyl-1,3 benzene two
Formic acid two heptyl ester；4-hydroxyl-1,3 phthalic acid two isocyanates；4-hydroxyl-1,3 dioctyl phthalates；4-hydroxyl
-1,3 phthalic acid di-isooctyls；4-hydroxyl-1,3 phthalic acid diphenyl esters；4-hydroxyl-1,3 phthalic acid dibenzyls
Ester；4-hydroxyl-1,3 phthalic acids are to chlorobenzene ester；4-hydroxyl-1,3 phthalic acids two are to tert-butyl group phenyl ester；4-
Hydroxyl-1,3 phthalic acid bicyclo-pentyl esters；4-hydroxyl-1,3 dicyclo-hexyl phthlates.
5. 4-hydroxyl-1 as described in claim 1,2,3 or 4,3 ester analog derivatives
Application, it is characterised in that be applied to UV absorbent, uvioresistant stabilizer or the system of synthetic spice
Standby.
6. 4-hydroxyl-1 as described in claim 1,2,3 or 4,3 ester analog derivatives
Application, it is characterised in that be applied to preparation medicine and pesticide as intermediate.
7. 4-hydroxyl-1 as claimed in claim 1, the preparation method of 3 ester analog derivatives,
It is characterized in that, preparation method is:
With raw material alcohol roh as solvent, dissolve 4-hydroxyl-1,3 phthalic acids, under ice bath, drip SOCl2, reaction
Temperature rising reflux after 1h, reacts complete evaporated under reduced pressure, adds ethyl acetate, with saturated sodium bicarbonate solution, satisfies
And brine It, drying, be evaporated to obtain crude product, after recrystallization white solid target compound 4-hydroxyl
-1,3 ester analog derivatives.
8. 4-hydroxyl-1 as claimed in claim 1, the preparation method of 3 ester analog derivatives,
It is characterized in that, preparation method is:
With raw material alcohol roh and DMF as solvent, dissolve 4-hydroxyl-1,3 phthalic acids, add catalyst
NaHSO4, backflow, react complete and be extracted with ethyl acetate, saturated sodium bicarbonate solution, saturated common salt are washed
Washing, drying, decompression except the raw alcohol of residual, obtains light yellow liquid targeted except solvent, crude product decompression distillation
Compound 4-hydroxyl-1,3 ester analog derivatives.
9. 4-hydroxyl-1 as claimed in claim 1, the preparation method of 3 ester analog derivatives,
It is characterized in that, preparation method is:
Being dissolved by 4-hydroxyl-isophathalic acid in DMF, ice-water bath is dividedly in some parts sodium hydride, and stirring is to no longer there being gas to produce
Raw, drip halogenated aryl hydrocarbon or halogenated hydrocarbons RX under room temperature, after reaction 1h, temperature rising reflux terminates to reaction；Reactant liquor cools down
In falling back, extracting with ether, saturated common salt is washed, drying, and decompression is except solvent afforded crude material, recrystallization
After white solid target compound 4-hydroxyl-1,3 ester analog derivatives.
Wherein RX refers to that halogenated aryl hydrocarbon or the halogenated hydrocarbons RX of the preceding paragraph, X are halogen.
10. 4-hydroxyl-1 as claimed in claim 1, the preparation side of 3 ester analog derivatives
Method, it is characterised in that preparation method is:
With raw material alcohol roh as solvent, add 4-hydroxyl-1,3 dimethyl phthalate and Feldalat NM, agitating heating
While steam the methanol of generation, reaction terminate after by the reactant liquor water of falling people, layering, take layer oily matter. use
20% acetum washing. then washing with water to neutrality, anhydrous magnesium sulfate is dried, and liquid target is distilled to obtain in decompression
Compound 4-hydroxyl-1,3 ester analog derivatives.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107935840A (en) * | 2017-12-05 | 2018-04-20 | 常州工程职业技术学院 | A kind of 4 Hydroxy M Phthalic Acid derivatives and synthetic method |
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