CN116536058A - Synthesis method of gemini surfactant and application of gemini surfactant in plant hair dye - Google Patents
Synthesis method of gemini surfactant and application of gemini surfactant in plant hair dye Download PDFInfo
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- CN116536058A CN116536058A CN202310439150.1A CN202310439150A CN116536058A CN 116536058 A CN116536058 A CN 116536058A CN 202310439150 A CN202310439150 A CN 202310439150A CN 116536058 A CN116536058 A CN 116536058A
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- gemini surfactant
- hydroquinone
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- acid
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 50
- 239000000118 hair dye Substances 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- -1 di (chloroacetic acid) hydroquinone ester Chemical class 0.000 claims abstract description 14
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 8
- 150000002193 fatty amides Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 31
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 9
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 claims description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 3
- 229940106681 chloroacetic acid Drugs 0.000 claims description 3
- 239000002274 desiccant Substances 0.000 claims description 3
- 238000004043 dyeing Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 9
- 150000008442 polyphenolic compounds Chemical class 0.000 abstract description 5
- 235000013824 polyphenols Nutrition 0.000 abstract description 5
- 125000003368 amide group Chemical group 0.000 abstract description 4
- 229940031728 cocamidopropylamine oxide Drugs 0.000 abstract description 4
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 239000000693 micelle Substances 0.000 abstract description 3
- 125000006850 spacer group Chemical group 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- 239000000230 xanthan gum Substances 0.000 description 6
- 229920001285 xanthan gum Polymers 0.000 description 6
- 229940082509 xanthan gum Drugs 0.000 description 6
- 235000010493 xanthan gum Nutrition 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000001819 mass spectrum Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- KXFJXWOTQMPQNI-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCN(C)C KXFJXWOTQMPQNI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CIWBSHSKHKDKBQ-SZSCBOSDSA-N 2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one Chemical compound OC[C@H](O)C1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-SZSCBOSDSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002211 L-ascorbic acid Substances 0.000 description 3
- 235000000069 L-ascorbic acid Nutrition 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 229940089960 chloroacetate Drugs 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- HSEMFIZWXHQJAE-UHFFFAOYSA-N hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(N)=O HSEMFIZWXHQJAE-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 1
- 244000147568 Laurus nobilis Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 235000021360 Myristic acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001143 laurus nobilis l. Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VJDHPVULCJEXHP-UHFFFAOYSA-N n-[2-(dimethylamino)ethyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCN(C)C VJDHPVULCJEXHP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
Classifications
-
- 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
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/42—Amides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/18—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/22—Amides or hydrazides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/28—Aminocarboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epidemiology (AREA)
- Birds (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of a gemini surfactant and application of the gemini surfactant in plant hair dye, and belongs to the field of surfactants. The invention utilizes the reaction of di (chloroacetic acid) hydroquinone ester with N- [2- (dimethylamino) ethyl ] fatty amide to prepare the gemini surfactant containing semi-rigid spacer groups, ester groups and amide groups. The gemini surfactant has the advantages of higher surface activity, lower critical micelle concentration, simple synthesis method, mild reaction condition, convenient operation and good application prospect. The gemini surfactant is compounded with cocamidopropyl amine oxide, is used for preparing plant hair dye, can reduce the dyeing temperature of plant hair dye containing polyphenol substances, and can improve the color fastness of dyed hair.
Description
Technical Field
The invention relates to the field of surfactants, in particular to a synthetic method of a gemini surfactant and application of the gemini surfactant in plant hair dyes.
Background
Along with the continuous pursuit of people on beauty, the hair dye industry has a great vitality and market development potential. The current oxidative hair dye mainly comprises p-phenylenediamine, o-phenylenediamine, p-aminophenol and derivatives thereof as dyes, and also comprises trace plant extracts as natural components or odor regulators. Therefore, development of natural, nontoxic, green and healthy plant hair dyes has become an important focus of attention for many scientists and consumers. Although the plant hair dye is safe and healthy, the plant hair dye has slow development due to the defects of complex extraction process, poor pigment stability, relatively complex dyeing process, higher production cost and the like, and has not been popularized and applied in the market. At present, polyphenol plant hair dye belongs to research hotspots, but the hair dye needs a higher temperature (about 50 ℃) to dye white hair with a satisfactory color, and the color of the white hair dyed at normal temperature (about 25 ℃) is very light.
Disclosure of Invention
The invention aims at: in order to reduce the harm of the surfactant to the environment, the biodegradability of the surfactant is increased, the vesicle is easier to form, and the aim of low-temperature stable dyeing is fulfilled.
In order to achieve the above purpose, the following technical scheme is provided:
the invention provides a gemini surfactant shown in the following structure,
wherein R is C n -1H 2n-1 ，n＝12-16。
In one embodiment of the present invention, the gemini surfactant comprises a semi-rigid spacer group, an ester group, and an amide group, and is prepared by the following method:
bis (chloroacetic acid) hydroquinone ester with N- [2- (dimethylamino) ethyl ]]Reacting fatty amide in solvent, recrystallizing after the reaction is finished, and recording the obtained gemini surfactant as n-E 2 Ph-n。
In one embodiment of the invention, the molar ratio of hydroquinone bis (chloroacetate) to N- [2- (dimethylamino) ethyl ] fatty amide is 1: (1.8-2.5).
In one embodiment of the invention, the concentration of hydroquinone bis (chloroacetate) relative to the solvent is from 0.5 to 2.0mmol/mL; specifically, 1.0mmol/mL is selected.
In one embodiment of the invention, the reaction time is from 10 to 48 hours.
In one embodiment of the present invention, the solvent is selected from one or a mixture of methanol, ethanol, ethyl acetate, water, chloroform, acetone.
In one embodiment of the invention, the solvent is specifically selected from a mixture of acetone and chloroform in a volume ratio of 1:1 to 5:1. And the specific selection ratio is 3:1.
In one embodiment of the invention, the hydroquinone bis (chloroacetate) is prepared by the process of:
dissolving hydroquinone, chloracetyl chloride and an acid binding agent in an organic solvent, reacting for 2-8 hours at the temperature of-10-20 ℃, adjusting the pH value to 7 after the reaction is finished, separating liquid, collecting an organic phase, drying by a drying agent, performing reduced pressure distillation to obtain a crude product, and recrystallizing the crude product by a mixed solvent to obtain a pure product of the hydroquinone ester of the bis (chloroacetic acid).
In one embodiment of the present invention, the organic solvent is selected from one or more of dichloromethane, chloroform, acetone.
In one embodiment of the invention, the acid binding agent is selected from one or more of pyridine, triethylamine, and potassium carbonate.
In one embodiment of the invention, the molar ratio of hydroquinone to chloroacetyl chloride is 1: (1.8-2.5).
In one embodiment of the invention, the chloroacetyl chloride can be added by dripping, and the dripping time is controlled within 30 minutes.
In one embodiment of the invention, the concentration of hydroquinone relative to the organic solvent is from 0.5 to 2.0mmol/mL; specifically, 1.0mmol/mL is selected.
In one embodiment of the invention, the molar ratio of hydroquinone to acid-binding agent is 1: (1.8-2.5).
In one embodiment of the invention, the reaction time is 2 to 8 hours.
In one embodiment of the invention, the organic solvent is a mixture of two of petroleum ether, acetone, ethyl acetate, ethanol and chloroform. Further optional acetone: petroleum ether mixed solvent; acetone of which: the volume ratio of petroleum ether is 1:1-5:1. The specific volume ratio is optionally 3:1.
In one embodiment of the present invention, the desiccant is selected from one or more of anhydrous calcium chloride, anhydrous sodium sulfate, anhydrous magnesium sulfate.
In one embodiment of the invention, an N- [2- (dimethylamino) ethyl ] fatty amide is prepared by:
dispersing fatty acid (RCOOH) in medium, heating for dissolving, adding 3-dimethylaminopropylamine, heating for reflux reaction, removing water generated in the reaction by using a water separator, removing excessive substances by reduced pressure distillation after the completion, and recrystallizing with petroleum ether for multiple times.
In one embodiment of the invention, the fatty acid (RCOOH) is selected from lauric acid, myristic acid, palmitic acid.
In one embodiment of the invention, the medium is selected from one or more of toluene, chloroform, methylene chloride.
In one embodiment of the invention, the molar ratio of fatty acid to 3-dimethylaminopropylamine is 1: (1.2-2.5); specifically, the ratio of the components is 1:1.5.
In one embodiment of the invention, the concentration of fatty acid in the medium is 0.5-2.0mmol/mL; specifically, 1.0mmol/mL is selected.
In one embodiment of the invention, the reflux reaction is carried out for a period of time of from 10 to 20 hours.
Meanwhile, the invention uses mass spectrum to carry out structural characterization on the target product.
The surface tension is an important property of a liquid and the ability of a surfactant to reduce the surface tension of water is an important parameter in evaluating its surface activity. The research adopts a K100 type (Germany) full-automatic surface tensiometer to measure the surface tension of a product aqueous solution, prepares a series of curves of the surface tension of the surfactant aqueous solution along with the change of concentration, and obtains a critical micelle concentration value (cmc) and the surface tension (gamma) under the critical micelle concentration from turning points of the curves in the graph cmc )。
The invention also provides a plant hair dye containing the gemini surfactant.
The invention also provides a preparation method of the plant hair dye, wherein the gemini surfactant is compounded with cocamidopropyl amine oxide to provide rigid cationic sites and interaction with polyphenol, so that the dye-uptake of the polyphenol plant pigment on hair can be increased, the interaction between the pigment and the hair is increased, and the plant hair dye with better color fastness is obtained.
In one embodiment of the present invention, the plant hair dye includes an agent a and an agent B; wherein the agent A comprises the following components: gallic acid, sodium hydroxide, xanthan gum, phenoxyethanol, the gemini surfactant, cocamidopropyl amine oxide and water; the agent B comprises the following components:
in one embodiment of the invention, the agent A comprises 1 to 20 percent of gallic acid, 0.1 to 0.8 percent of sodium hydroxide, 1.5 to 2.5 percent of xanthan gum, 0.2 to 6 percent of phenoxyethanol, 0.2 to 0.5 percent of the gemini surfactant, 0.2 to 0.5 percent of cocamidopropyl amine oxide and the balance of water.
In one embodiment of the present invention, the agent B contains Fe 2+ 3.5 to 7.5 percent of mordant, 7 3 to 5 percent of polyquaternium-7 3 to 0.05 percent of L (+) -ascorbic acid, 3 to 5 percent of dimethyl diallyl ammonium chloride and distilled water to 100 percent.
Compared with the prior art, the invention has the following beneficial effects:
the invention is simple and mild to prepare a series of novel cationic gemini surfactants containing semi-rigid spacer groups and amide groups; the gemini surfactant obtained by the invention has excellent surface activity, contains ester groups and amide groups and has good biodegradability.
The gemini surfactant of the invention introduces a gemini surfactant with benzene rings, which can reduce the influence of repulsive force between cations through the action of rigid cations and hair, and simultaneously compared with the prior gemini surfactant (CN 111039818A), the introduced benzene rings can act with polyphenol, can deepen the color depth of white hair dyeing at normal temperature, can dye hair at lower temperature, and has good color fastness after dyeing.
Drawings
FIG. 1 is a synthetic route diagram of gemini surfactants of the present invention;
FIG. 2 is 12-E 2 Nuclear magnetic hydrogen spectrogram of Ph-12;
FIG. 3 is 14-E 2 Nuclear magnetic hydrogen spectrogram of Ph-14;
FIG. 4 is 16-E 2 Nuclear magnetic hydrogen spectrogram of Ph-16;
FIG. 5 is 12-E 2 Mass spectrum of Ph-12;
FIG. 6 is 14-E 2 Mass spectrum of Ph-14;
FIG. 7 is 16-E 2 A mass spectrum of the Ph-16 mass spectrum;
FIG. 8 shows the gamma-lgC curve (25 ℃) for the target product according to the invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
(1) Preparation of hydroquinone bis (chloroacetate):
0.1mol of hydroquinone and 0.22mol of chloracetyl chloride are reacted in 100ml of solvent dichloromethane, 0.22mol of pyridine is added as an acid binding agent, the reaction is carried out for 4 hours at 0 ℃, after the reaction is finished, the pH is regulated to 7 by using sodium bicarbonate saturated solution, the organic phase is obtained by drying anhydrous sodium sulfate after liquid separation, the crude product is obtained by reduced pressure distillation, and the crude product is obtained by acetone: recrystallizing the petroleum ether mixed solvent in a ratio of 3:1 to obtain a pure product, namely obtaining the hydroquinone bis (chloroacetate) (intermediate 1);
(2) Preparation of intermediate N- [2- (dimethylamino) ethyl ] lauramide:
adding 100mL of toluene serving as a solvent and 0.1mol of lauric acid into a three-neck round bottom flask, heating and refluxing for 10 hours after the oil bath temperature reaches 80 ℃ to dissolve the lauric acid, adding 0.15mol of 3-dimethylaminopropylamine, removing water generated in the reaction by adopting a water separator, removing redundant substances by reduced pressure distillation after the completion, and recrystallizing the product with petroleum ether for multiple times to obtain N- [2- (dimethylamino) ethyl ] lauramide;
(3) Preparation of gemini surfactant:
0.22mol of N- [2- (dimethylamino) ethyl group]Laurel (Laurus nobilis L.) LinneDissolving amide in 100mL of chloroform solvent, reacting with 0.1mol of intermediate 1 at 65 ℃ for 12h, removing the solvent by a rotary evaporator after the reaction, recrystallizing in a mixed solvent of acetone and chloroform (the mixed volume ratio of the acetone to the chloroform is 3:1), precipitating, and drying to obtain a target product, namely the gemini surfactant, which is marked as 12-E 2 Ph-12；
Product 12-E 2 Characterization of Ph-12:
1 H NMR(400MHz,CDCl3)δppm:8.04(s,2H,-2CONH-),7.14(s,4H,-ArH-),5.40(s,4H,-2N + CH 2 COOAr-),3.94(s,4H,-2N + CH 2 CH 2 -),3.55(d,J＝39.3Hz,12H,-2CH 2 N + (CH 3 ) 2 -),3.33(s,4H,-2CH 2 CH 2 NHCO-),2.25(t,J＝7.3Hz,4H,-2CH 2 CONH-),2.13(s,4H,-2CH 2 CH 2 NHCO-),1.57(s,4H,-2CH 2 CH 2 CONH-),1.33–1.13(m,32H,-2CH 3 (CH 2 ) 8 -),0.87(t,J＝6.9Hz,6H,2CH 3 (CH 2 ) 8 -)
MS(ESI)positive ions m/z:759calculated for(M-2Cl-H) + ,380calculated for(M-2Cl) 2+ /2。
example 2
(1) Preparation of hydroquinone bis (chloroacetate):
0.1mol of hydroquinone and 0.3mol of chloracetyl chloride are reacted in 100mL of acetone solvent, 0.3mol of triethylamine is added as an acid binding agent, the reaction is carried out for 6 hours at the temperature of minus 5 ℃, the pH value is regulated to 7 by sodium bicarbonate saturated solution after the reaction is finished, anhydrous magnesium sulfate is used for drying after liquid separation, an organic phase is obtained, the organic phase is distilled under reduced pressure, and a crude product is obtained, and the crude product is obtained by acetone: recrystallizing the petroleum ether mixed solvent in a ratio of 3:1 to obtain a pure product, namely obtaining the hydroquinone bis (chloroacetate) (intermediate 1);
(2) Preparation of intermediate N- [2- (dimethylamino) ethyl ] myristamide:
adding 100mL of solvent toluene and 0.1mol of myristic acid into a three-necked round bottom flask, wherein the temperature of an oil bath reaches 80 ℃ to dissolve the myristic acid, adding 0.15mol of 3-dimethylaminopropylamine, heating and refluxing for 11h, removing water generated in the reaction by adopting a water separator, removing redundant substances by reduced pressure distillation after the completion, and recrystallizing the product with petroleum ether for multiple times to obtain N- [2- (dimethylamino) ethyl ] lauramide;
(3) Preparation of gemini surfactant:
0.22mol of N- [2- (dimethylamino) ethyl group]Dissolving cinnamamide in 100mL ethyl acetate solvent, reacting with 0.1mol intermediate 1 at 80deg.C for 8 hr, removing solvent by rotary evaporator after reaction, recrystallizing in mixed solvent of acetone and chloroform (the mixed volume ratio of acetone and chloroform is 4:1), precipitating, drying to obtain target product, and recording as 14-E 2 Ph-14。
Product 14-E 2 Characterization of Ph-14:
1 H NMR(400MHz,CDCl3)δppm:8.05(s,2H,-2CONH-),7.17(s,4H,-ArH-),5.31(s,4H,-2N + CH 2 COOAr-),3.89(s,4H,-2N + CH 2 CH 2 -),3.46(s,12H,-2CH 2 N + (CH 3 ) 2 -),3.31(s,4H,-2CH 2 CH 2 NHCO-),2.24(t,J＝7.2Hz,4H,2CH 2 CONH),2.11(s,4H,-2CH 2 CH 2 NHCO-),1.57(s,4H,-2CH 2 CH 2 CONH-),1.02–1.33(m,40H,-2CH 3 (CH 2 ) 10 -),0.87(t,J＝6.8Hz,6H2CH 3 (CH2) 10 -)
MS(ESI)positive ions m/z:815calculated for(M-2Cl-H) + ,408calculated for(M-2Cl) 2+ /2。
example 3
(1) Preparation of hydroquinone bis (chloroacetate):
0.1mol of hydroquinone and 0.22mol of chloracetyl chloride are reacted in 100ml of methylene dichloride solvent, meanwhile, 0.22mmol of triethylamine is added as an acid binding agent, the reaction is carried out for 4 hours at 0 ℃, after the reaction is finished, a saturated solution of sodium bicarbonate is used for adjusting the pH value to 7, anhydrous calcium chloride is used for drying after liquid separation, an organic phase is obtained, the organic phase is distilled under reduced pressure, and a crude product is obtained, and the crude product is obtained by acetone: recrystallizing the petroleum ether mixed solvent in a ratio of 3:1 to obtain a pure product, namely obtaining the hydroquinone bis (chloroacetate) (intermediate 1);
(2) Preparation of intermediate N- [2- (dimethylamino) ethyl ] palmitamide:
adding 100mL of toluene solvent and 0.1mol of palmitic acid into a three-neck round bottom flask, wherein the oil bath temperature reaches 80 ℃ to dissolve the palmitic acid, adding 0.15mol of 3-dimethylaminopropylamine, heating and refluxing for 12 hours, removing water generated in the reaction by adopting a water separator, removing redundant substances by reduced pressure distillation after the completion, and recrystallizing the product with petroleum ether for multiple times to obtain N- [2- (dimethylamino) ethyl ] lauramide;
(3) Preparation of gemini surfactant:
0.22mmol of N- [2- (dimethylamino) ethyl group]Dissolving palmitoamide in 100mL of chloroform solvent, reacting with 0.1mol of intermediate 1 at 65 ℃ for 24 hours, removing the solvent by a rotary evaporator after the reaction, recrystallizing in a mixed solvent of acetone and chloroform (the mixed volume ratio of the acetone to the chloroform is 5:1), precipitating, drying to obtain a target product, and recording as 16-E 2 Ph-16。
Product 16-E 2 Characterization of Ph-16:
1 H NMR(400MHz,CDCl3)δppm:8.02(s,2H,-2CONH-),7.19(s,4H,-ArH-),5.22(s,4H,-2N + CH 2 COOAr-),3.84(s,4H,-2N + CH 2 CH 2 -),3.43(s,12H,-2CH 2 N + (CH 3 ) 2 -),3.29(s,4H,-2CH 2 CH 2 NHCO-),2.23(t,4H,-2CH 2 CONH-),2.09(s,4H,-2CH 2 CH 2 NHCO-),1.56(s,4H,-2CH 2 CH 2 CONH-),1.27(dd,48H,-2CH 3 (CH 2 ) 12 -),0.88(t,J＝6.8Hz,6H 2CH 3 (CH2) 12 -)
MS(ESI)positive ions m/z:871calculated for(M-2Cl-H) + ,436calculated for(M-2Cl) 2+ /2
example 4
The A agent comprises the following components:
and (3) preparation of an agent A: mixing all materials except xanthan gum, dissolving in water solution, adjusting pH to 8.00 with sodium hydroxide, placing the solution into a high-speed stirrer, adding xanthan gum while stirring, stirring for dissolving to obtain gel A, and storing in refrigerator at 4deg.C.
And (3) preparation of a B agent: 5% of mordant, 3.5% of polyquaternium-7, 0.02% of L (+) -ascorbic acid, 3% of dimethyl diallyl ammonium chloride and 100% of distilled water. Firstly, completely dissolving the polyquaternium-7 in distilled water, then adding other residual components, and uniformly mixing to obtain the hair dye B agent.
The dyeing method comprises the following steps: the agent A is extruded into foam by a foam bottle, smeared on white hair, and is washed by clean water after staying for half an hour. And then the agent B is smeared, the cleaning is carried out after the agent B stays for half an hour, and the dyeing is finished. The corresponding hair dyeing effect is shown in Table 1.
TABLE 1 results of dyeing with different formulations A
| Formulation A | Formula I-1 | Formula I-2 | Formula I-3 | Formula I-4 |
| Hair dyeing effect (25 ℃ C.) | Hair is not colored | Light blue hair | Blue-black hair | Blue-black hair |
Replacement of Gemini surface in formulation I-3The active agent is 12-E 2 Ph-12、16-E 2 Ph-16, the others were unchanged and the corresponding hair dyeing results are shown in Table 2.
TABLE 2
| Gemini surfactants | 12-E 2 Ph-12 | 16-E 2 Ph-16 |
| Hair dyeing effect (25 ℃ C.) | Blue-black hair | Blue-black hair |
Example 5
The A agent comprises the following components:
and (3) preparation of an agent A: mixing all materials except xanthan gum, dissolving in water solution, adjusting pH to 8.00 with sodium hydroxide, placing the solution into a high-speed stirrer, adding xanthan gum while stirring, stirring for dissolving to obtain gel A, and storing in refrigerator at 4deg.C.
And (3) preparation of a B agent: 5% of mordant, 3.5% of polyquaternium-7, 0.02% of L (+) -ascorbic acid, 3% of dimethyl diallyl ammonium chloride and 100% of distilled water. Firstly, completely dissolving the polyquaternium-7 in distilled water, then adding other residual components, and uniformly mixing to obtain the hair dye B agent.
The dyeing method comprises the following steps: the agent A is extruded into foam by a foam bottle, smeared on white hair, and is washed by clean water after staying for half an hour. And then the agent B is smeared, the cleaning is carried out after the agent B stays for half an hour, and the dyeing is finished. The corresponding hair dyeing effect is shown in Table 3.
TABLE 3 results of dyeing with different formulations A
| Formulation A | Formula II-1 | Formula II-2 | Formula II-3 | Formula II-4 |
| Hair dyeing effect (25 ℃ C.) | Hair is not colored | Light blue hair | Blue-black hair | Blue-black hair |
The amount of gemini surfactant used in alternative formulation II-3 was 0.1% and 1.0%, the others were unchanged and the corresponding hair dyeing results are shown in Table 4.
TABLE 4 Table 4
| Gemini surfactant dosage | 0.1％ | 0.5％ | 1.0 |
| Hair dyeing effect (25 ℃ C.) | Light blue hair | Blue-black hair | Colorless hair |
The gemini surfactant of the structure shown in formula 1 mentioned above:
the above examples are not intended to limit the scope of the invention nor the order of execution of the steps described. The present invention is obviously modified by a person skilled in the art in combination with the prior common general knowledge, and falls within the scope of protection defined by the claims of the present invention.
Claims (10)
1. A gemini surfactant shown in the following structure,
wherein R is C n -1H 2n-1 ，n＝12-16。
2. The gemini surfactant according to claim 1, wherein the gemini surfactant is prepared by the following method:
double%Chloroacetic acid) hydroquinone ester with N- [2- (dimethylamino) ethyl]Reacting fatty amide in solvent, recrystallizing after the reaction is finished, and recording the obtained gemini surfactant as n-E 2 Ph-n。
3. The gemini surfactant according to claim 2, wherein the molar ratio of hydroquinone bis (chloroacetate) to N- [2- (dimethylamino) ethyl ] fatty amide is 1: (1.8-2.5).
4. The gemini surfactant according to claim 2, wherein the concentration of hydroquinone bis (chloroacetate) relative to the solvent is 0.5-2.0mmol/mL.
5. The gemini surfactant of claim 2, wherein the solvent is selected from one or a mixture of methanol, ethanol, ethyl acetate, water, chloroform, acetone.
6. The gemini surfactant according to claim 2, wherein the hydroquinone bis (chloroacetate) is prepared by:
dissolving hydroquinone, chloracetyl chloride and an acid binding agent in an organic solvent, reacting for 2-8 hours at the temperature of-10-20 ℃, adjusting the pH value to 7 after the reaction is finished, separating liquid, collecting an organic phase, drying by a drying agent, performing reduced pressure distillation to obtain a crude product, and recrystallizing the crude product by a mixed solvent to obtain a pure product of the hydroquinone ester of the bis (chloroacetic acid).
7. The gemini surfactant of claim 6, wherein the molar ratio of hydroquinone to chloroacetyl chloride is 1: (1.8-2.5); the concentration of hydroquinone relative to the organic solvent is 0.5-2.0mmol/mL; the mol ratio of hydroquinone to acid-binding agent is 1: (1.8-2.5).
8. The gemini surfactant according to claim 2, wherein the N- [2- (dimethylamino) ethyl ] fatty amide is prepared by:
dispersing fatty acid (RCOOH) in medium, heating for dissolving, adding 3-dimethylaminopropylamine, heating for reflux reaction, removing water generated in the reaction by using a water separator, removing excessive substances by reduced pressure distillation after the completion, and recrystallizing with petroleum ether for multiple times.
9. The gemini surfactant of claim 8, wherein the molar ratio of fatty acid to 3-dimethylaminopropylamine is 1: (1.2-2.5); the concentration of fatty acid in the medium is 0.5-2.0mmol/m.
10. A plant hair dye comprising the gemini surfactant of any one of claims 1-9.
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