JPS648634B2 - - Google Patents
Info
- Publication number
- JPS648634B2 JPS648634B2 JP55099449A JP9944980A JPS648634B2 JP S648634 B2 JPS648634 B2 JP S648634B2 JP 55099449 A JP55099449 A JP 55099449A JP 9944980 A JP9944980 A JP 9944980A JP S648634 B2 JPS648634 B2 JP S648634B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- alkyl
- reaction
- compound according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 150000001875 compounds Chemical class 0.000 claims description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 150000003512 tertiary amines Chemical class 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000011541 reaction mixture Substances 0.000 description 14
- -1 halogen ions Chemical class 0.000 description 13
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 210000004209 hair Anatomy 0.000 description 8
- 239000004744 fabric Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001461 argentometric titration Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002453 shampoo Substances 0.000 description 3
- 150000005691 triesters Chemical class 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 2
- 229950010007 dimantine Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- BKRJTJJQPXVRRY-UHFFFAOYSA-M dodecyl-(2-hydroxyethyl)-dimethylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCO BKRJTJJQPXVRRY-UHFFFAOYSA-M 0.000 description 2
- CWILBLFCNWVURT-UHFFFAOYSA-N n,n-diethylethanamine;octadecanamide Chemical compound CCN(CC)CC.CCCCCCCCCCCCCCCCCC(N)=O CWILBLFCNWVURT-UHFFFAOYSA-N 0.000 description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- UCWYGNTYSWIDSW-QXMHVHEDSA-N (z)-n-[3-(dimethylamino)propyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCCN(C)C UCWYGNTYSWIDSW-QXMHVHEDSA-N 0.000 description 1
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical class CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- YJHSJERLYWNLQL-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)CCO YJHSJERLYWNLQL-UHFFFAOYSA-N 0.000 description 1
- QOLLYDAQOZBRAL-UHFFFAOYSA-M 2-hydroxyethyl-dimethyl-octadecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCO QOLLYDAQOZBRAL-UHFFFAOYSA-M 0.000 description 1
- 238000009631 Broth culture Methods 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N aniline-p-carboxylic acid Natural products NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229960001927 cetylpyridinium chloride Drugs 0.000 description 1
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ICZKASVWFUJTEI-UHFFFAOYSA-N n,n-dimethyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN(C)C ICZKASVWFUJTEI-UHFFFAOYSA-N 0.000 description 1
- AYNZRGVSQNDHIX-UHFFFAOYSA-N n,n-dimethylicosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN(C)C AYNZRGVSQNDHIX-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DNVLJEWNNDHELH-UHFFFAOYSA-N thiocyclam Chemical compound CN(C)C1CSSSC1 DNVLJEWNNDHELH-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 239000006150 trypticase soy agar Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
- A61Q5/02—Preparations for cleaning the hair
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
-
- 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
- A61K8/55—Phosphorus compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Dentistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
本発明は、新規なリン誘導体に関する。さらに
詳しくは、本発明は、式
で表わされ、式中、
R1が低級アルキレンまたはヒドロキシ低級ア
ルキレンであり、
R2とR3が低級アルキルであり、そして
Aが直鎖または分岐C12―22アルキルまたは式
―R4―NHCO―R5で表わされ、式中、
R4が低級アルキレンであり
R5がC12―22アルキルである
基であり、
Xがハロゲンである
化合物。に関する。
本発明の新規な化合物は、次の方法を包含する
いくつかの方法によつて製造できる:
方法A:ヒドロキシル基含有第四アンモニウム化
合物とオキシ塩化リンとの反応
一般式NR2R3―A(R2,R3,Aは上記の通り)
で表わされる第三アミンをX―R1―OH(R1,X
は上記の通り)で表わされる化合物で、適当な溶
媒、反応装置および反応条件を用いて、第四級化
する。さらに詳しくは、第四級化反応は、加熱
器、オーバーヘツドかきまぜ機、温度計および還
流冷却器を備えるガラス製またはガラスでライニ
ングした反応器内で、良好な混合および温度制御
を確保するために低級アルコール、水またはそれ
らの混合物のような溶媒を用いて、実施する。反
応温度は約70℃〜120℃の範囲であることができ
るが、一般に反応混合物の還流温度によつて支配
される。反応の進行は、第四級化の間に形成する
ハロゲンイオンの銀滴定の定量によつて監視す
る。図式的には、この反応は次のように示すこと
ができる:
第四アンモニウム化合物を単離するために、溶
媒の一部分を蒸留し、そして反応混合物を40〜50
℃に維持しながらアセトンを加える。冷却する
と、結晶性沈殿が形成し、これを吸引過し、真
空乾燥して単離する。
この反応の第2工程は、図式的に次のように示
すことができる:
ヒドロキシル基含有第四アンモニウム化合物と
オキシ塩化リンとの反応は、一般に低沸点の低極
性溶媒、たとえば、塩化メチレン中に第四アンモ
ニウム化合物を分散させ、そして必要なオキシ塩
化リンを一般に室温で加えることによつて、実施
する。いつたんすべてのオキシ塩化リンを加えた
後、温度を反応混合物の沸点に上昇させ、そして
混合物を18時間まで還流する。溶媒は蒸留により
回収し、そしてリン酸トリエステルを熱アセトン
からの再結晶により精製する。
有効であることがわかつた他の方法は、次のと
おりである:
方法B:第三アミンとハロゲン化ホスフエートエ
ステルとの反応
初期工程、すなわち、ホスフエートエステル中
間体は、次のように図式的に示すことができる:
式中Xはハロゲン官能基であり、そしてYは12
炭素原子までのアルキレン基であり、該アルキレ
ン基は3酸素原子までによつて中断されていても
よく、そして10炭素原子までの低級アルキル、ア
ルコキシ、ヒドロキシまたはヒドロキシアルキル
基で置換されていてもよい。
引き続く工程、すなわち、ホスフエートエステ
ルと第三アミンとの反応は図式的に次のように示
すことができる:
一般に、反応はオーバーヘツドかきまぜ機、滴
下漏斗、還流冷却器と外部の加熱および冷却単位
装置を備えるガラス反応器中で実施する。3部の
置換オキシラン、
The present invention relates to novel phosphorus derivatives. More specifically, the present invention provides the formula represented by the formula, R 1 is lower alkylene or hydroxy lower alkylene, R 2 and R 3 are lower alkyl, and A is straight chain or branched C 12 - 22 alkyl or the formula -R 4 -NHCO -A compound represented by R5 , in which R4 is lower alkylene , R5 is C12-22 alkyl, and X is halogen. Regarding. The novel compounds of the present invention can be prepared by several methods, including the following methods: Method A: Reaction of a hydroxyl group-containing quaternary ammonium compound with phosphorus oxychloride General formula NR 2 R 3 -A ( R 2 , R 3 , A are as above)
A tertiary amine represented by X--R 1 --OH (R 1 ,
(as described above) is quaternized using an appropriate solvent, reaction apparatus, and reaction conditions. More specifically, the quaternization reaction is carried out in a glass or glass-lined reactor equipped with a heater, an overhead stirrer, a thermometer and a reflux condenser to ensure good mixing and temperature control. It is carried out using solvents such as lower alcohols, water or mixtures thereof. The reaction temperature can range from about 70°C to 120°C, but is generally governed by the reflux temperature of the reaction mixture. The progress of the reaction is monitored by argentometric determination of the halogen ions formed during the quaternization. Diagrammatically, this reaction can be shown as follows: To isolate the quaternary ammonium compound, a portion of the solvent is distilled and the reaction mixture is
Add acetone while maintaining at °C. On cooling, a crystalline precipitate forms which is filtered off with suction and isolated by vacuum drying. The second step of this reaction can be shown diagrammatically as follows: The reaction of a hydroxyl-containing quaternary ammonium compound with phosphorus oxychloride generally involves dispersing the quaternary ammonium compound in a low boiling point, low polar solvent, such as methylene chloride, and adding the required phosphorus oxychloride, generally at room temperature. Implemented by. Once all the phosphorous oxychloride has been added, the temperature is raised to the boiling point of the reaction mixture and the mixture is refluxed for up to 18 hours. The solvent is recovered by distillation and the phosphoric triester is purified by recrystallization from hot acetone. Other methods found to be effective are as follows: Method B: Reaction of tertiary amine with halogenated phosphate ester The initial step, i.e. the phosphate ester intermediate, is schematically shown as follows: It can be shown that: where X is a halogen functional group and Y is 12
an alkylene group of up to carbon atoms, which alkylene group may be interrupted by up to 3 oxygen atoms and may be substituted with lower alkyl, alkoxy, hydroxy or hydroxyalkyl groups of up to 10 carbon atoms . The subsequent step, namely the reaction of the phosphate ester with the tertiary amine, can be illustrated schematically as follows: Generally, the reaction is carried out in a glass reactor equipped with an overhead stirrer, addition funnel, reflux condenser and external heating and cooling units. 3-part substituted oxirane,
【式】を反応器に
入れ、そして激しくかきまぜながら、1部の濃リ
ン酸を滴々加える。リン酸の添加速度を調整して
反応温度を65〜95℃、好ましくは85〜90℃に保
つ。ハロゲン含有エピビホスフエート中間体が生
成する。3部の適当な第三アミンを少しずつ加
え、その間反応温度を90〜100℃の間に保つ。ア
ミンを完全に添加した後、反応混合物を100〜120
℃に、アリコート部分の銀滴定が反応の完結を示
すまで、加熱する。
冷却後、反応混合物を熱メタノール/アセトン
中に溶かす。所望生成物は、メタノール/アセト
ン溶液の冷却により形成した沈殿を単離し、乾燥
して、得られる。
本発明の新規なリン酸トリエステル化合物は、
陽イオン性界面活性剤であり、そして髪の毛また
は他の負に帯電した表面上へ容易に収着されて静
電相互作用を減少できる。R4,R5またはR6が16
炭素原子より多い炭素骨格を有する場合、このよ
うな化合物を髪の毛に施こすと、“風になびく”
のが減少し、そして湿潤および乾燥した状態の梳
毛はきわめて良好となる。
通常、陽イオン性第四アンモニウム塩は広い範
囲の他の界面活性剤と容易に相溶しない。驚ろく
べきことには、本発明の新規な化合物は、広範囲
の界面活性剤、たとえば、ラウリル硫酸ナトリウ
ム型またはラウリルエーテル硫酸ナトリウム型の
陰イオン性界面活性剤;ベタイン、サルテインお
よびホスホベタインのような両性界面活性剤;エ
トキシル化ソルビタンエステルのような非イオン
性界面活性剤と容易に相溶する。この予期されな
い相溶性のため、本発明の化合物は普通のシヤン
プーおよびクリーム・リンス配合物に容易に混入
できる。本発明の化合物は、それを利用する組成
物に依存して、約0.1〜約20重量%の量で使用で
きる。20重量%より多い量を使用する場合、生ず
る組成物はシヤンプーまたはクリーム・リンスと
して使用するとき、手触りが悪く、刺激的である
ことがある。
さらに、本発明の新規なリン酸トリエステル化
合物の式(10負)中、AまたはAの構成部分であ
るR5が8〜14炭素原子の炭素鎖長であるとき、
これらの化合物は顕著な制菌性および殺菌性を示
す。これらの性質を有する化合物は、全組成物の
約0.1〜約5.0重量%で使用できる。約0.1%より少
ない量を使用する場合、所望の性質を得ることが
でき、そして約5.0%より大きい量を使用する場
合、得られる組成物は手触りが悪く、刺激的であ
ることがある。
次の実施例により本発明を説明する。
実施例
オーバーヘツドかきまぜ機、水冷凝縮器、滴下
漏斗、温度計および加熱マントルを備える500ml
容のガラス反応器に、46.53gのエピクロルヒド
リンを入れる。次いで19.0gの85.5%のリン酸
を、滴下漏斗を経て激しくかきまぜながら、温度
を80〜85℃に維持するように添加速度を調整し
て、加える。発熱反応が止んだ時、反応器を加熱
して反応混合物を80℃に1時間保持する。次いで
148gのオクタデシルジメチルアミンを反応器に
加え、そしてこの混合物を20時間102℃でかきま
ぜる。反応の完結は、発生した塩素イオンの銀滴
定により確認される。
ほぼ40℃に冷却した後、反応混合物を200mlの
エタノールで希釈し、2容のビーカーに移し、
1000mlのアセトンを加える。黄かつ色の沈殿が形
成し、これを吸引過により単離し、エタノー
ル/アセトン混合物から再結晶すると、黄かつ色
粉末が生ずる。塩素イオンの銀滴定およびけん化
の検定は、この物質が98.6%の純度であることを
示す。この生成物は、次の構造式の新規なリン酸
トリエステルを含有する:
実施例
実施例に記載するガラス反応器を用い、
93.52gのエピクロルヒドリンを38gの85.5%の
リン酸と85〜90℃において2時間反応させる。次
いで213.2gのドデシルジメチルアミンを3時間
かけて、温度を85〜90℃に保ちながら、加える。
100±5℃にさらに72時間加熱すると、90%より
高い反応の完結を示す塩素イオンについての銀滴
定値が得られる。反応生成物を実施例の手順に
従い単離すると、薄黄かつ色の自由流動性の粉末
が生じ、検定すると純度は99.0%である。この生
成物は、次の構造のリン酸のトリエステルを含有
する:
実施例
実施例に記載する装置を用い、19.0gの濃リ
ン酸を46.53gのエピクロルヒドリンに、反応温
度を85〜90℃に保ちながら、滴々加える。
176.5gのエイコシルジメチルアミンとドコシ
ルジメチルアミンの溶融50/50混合物を、温度を
100℃に保ちながら、2時間かけて加える。100℃
でさらに12時間後、反応混合物の温度を90分間
140℃に上昇する。
冷却後所望生成物を、熱エタノールから結晶
し、吸引過し、乾燥することによつて、単離す
る。銀滴定によると、活性は94.6%である。
構造は、C12H25置換基がC20H41とC22H45との
1:1の比の混合基で置換されている以外、実施
例の構造と同一である。
実施例
オーバーヘツドかきまぜ機と還流冷却器を備え
る2のガラス反応器を用い、140.28gのエピク
ロルヒドリンを57gの85.5%のリン酸と反応さ
せ、そしてこの反応を85〜90℃で2時間かきまぜ
る。この反応生成物に、548.6gの3―オレオア
ミドプロピルジメチルアミンを加え、温度を95〜
100℃に上昇する。22時間後、銀滴定は反応が完
結に近づいていることを示し、反応混合物を冷却
する。エタノール/アセトンからの結晶、吸引
過および乾燥後、灰色粉末が得られる。この生成
物は、次の構造の新規なリン酸トリエステルを含
有する:
実施例
実施例に記載する反応器と反応条件を用い、
112.2gのエピクロルヒドリンを45.6gの85.5%の
リン酸と反応させる。次いで、458.4gのステア
ラミドエチルジエチルアミンを反応混合物に加
え、この反応混合物を95℃に20時間維持する。反
応の完結は銀滴定により推定し、そして反応生成
物は次の構造の新規なリン酸トリエステルを含有
する:
実施例
297gのオクタデシルジメチルアミンと80gの
エチレンクロルヒドリンを無水エタノールに溶か
して、全体の体積を1500mlとする。次いでこの混
合物を、還流冷却器を備える2容の丸底フラス
コ中で加熱する。6日後、塩素イオンの滴定は反
応が91%完結したことを示し、そして反応を停止
する。所望のステアリルジメチル―2―ヒドロキ
シエチルアンモニウムクロリドを、アセトンで沈
殿させて単離する。エタノール/アセトン混合物
からの再結晶、過および真空乾燥後、白色粉末
が得られ、これを塩素イオンについて滴定する
と、98.9%の純度であると検定される。
次いで、このステリルジメチル―2―ヒドロキ
シエチルアンモニウムクロリドの228.7gを、オ
ーバーヘツドかきまぜ機、滴下漏斗と還流冷却器
を備える2容の三首丸底フラスコに入れる。
1200mlの塩化メチレンを加え、第四アンモニウム
化合物を激しくかきまぜながら分散する。30.70
gのオキシ塩化リン、POCl3、を1時間かけて
滴々加える。次いで、この反応混合物を18時間還
流し、塩化メチレンを蒸留により除去し、このト
リエステルを熱アセトンからの再結晶により精製
する。
この生成物は、次の構造の新規なリン酸トリエ
ステルを含有する:
実施例
213.14gのドデシルジメチルアミンを1200mlの
無水エタノール中に溶かし、80gのエチレンクロ
ルヒドリンを加え、生ずる反応混合物を72時間か
きまぜる。ドデシルジメチル―2―ヒドロキシエ
チルアンモニウムクロリドが、アセトンによる沈
殿、エタノール/アセトンによる再結晶、過お
よび真空乾燥後、84%の収率で得られる。175.9
gの上のドデシルジメチル―2―ヒドロキシエチ
ルアンモニウムクロリドを30.70gのオキシ塩化
リンと、実施例に記載する装置および反応条件
を用いて、反応させる。
この生成物は、次の構造の新規なリン酸トリエ
ステルを含有する:
実施例
305.6gのステアラミドエチルジエチルアミン
を2000mlの無水エタノール中に溶かす。次いで64
gのエチレンクロルヒドリンを加え、この反応混
合物を120時間還流する。次いでエタノールのほ
ぼ4分の3をフラツシユ蒸発により除去し、アセ
トンを沸点において飽和まで加え、この反応混合
物を室温に冷却する。形成した白色の沈殿を単離
し、真空乾燥し、そしてステアラミドエチルジエ
チル―2―ヒドロキシエチルアンモニウムクロリ
ドとして確認される。
277.2gのこのステアラミドエチルジエチル―
2―ヒドロキシエチルアンモニウムクロリドを
30.7gのオキシ塩化リンと、実施例に記載する
装置および反応条件を用いて、反応させる。この
生成物は、次の構造の新規なリン酸トリエステル
を含有する:
実施例
ヘアケアー(hair care)製品を、次のように
して調製する:
次の構造
式中Rは1:1の比のC11―C13混合基である、
のホスホベタインの30%活性溶液の150重量部を、
200部の蒸留水と周囲温度において加え、次いで
実施例の陽イオン性トリホスフエートエステル
の26%活性溶液の77重量部を加え、生ずる溶液を
透明かつ均質になるまで混合する。次いで、米国
特許第2970160号中に記載される方法により製造
し、次式
式中Rは1:1の比のC11―C13混合基である、
で表わされる両性物質の30%活性溶液の150重量
部を加える。次いで200部の72%ポリオキシエチ
レン(80)ソルビタンモノココエートを加え、次
いで12gのポリエチレングリコール6000ジステア
レートを加え、生ずる混合物を70℃に20分間かき
まぜる。この溶液を35℃に冷却し、15%HCl溶液
でPHを7.0±1に調整する。防腐剤と香料を加え、
十分な量の脱イオン水で全体を1000gとする。
最終製品は透明であり、25℃においてブルツク
フイールド粘度計で#2スピンドルを用い12rpm
で測定した粘度が1225cpsである。この製品はき
わめてすぐれた発泡とクリーニング性質を示し、
ビユーテイ・サロンのハーフ・ヘツド(half
head)研究で確認されるように髪の毛について
コンデイシヨニング効果を示す。これらの研究は
各被験者の髪の毛を2つの部分に分離し、一方の
部分に本発明の新規な化合物を含有するシヤンプ
ー組成物で処理し、他方の部分を新規な化合物を
含まない同じ組成物で処理し、そして同じガイド
ラインに従つて結果を主観的に等級づける。
実施例
次の洗剤のヘアクレンザーまたはスキンクレン
ザーを、実施例中に概説した手順に従い調製す
る:
成 分 重量/重量%
ココアミドプロピルサルタミン 5.00
トリデシルエーテル(4)サルフエート 5.00
トリス―ステアリルアミノホスフエートエステ
ル 0.30
プロピレングリコール 1.00
増粘剤 2.00
防腐剤 0.10
染 料 0.02
香 料 0.20
脱イオン水を加えて 100%
上のPHを希HClで5.5に調製した。
実施例 XI
クリーナ、ソフナーおよび衛生化組成物を、次
の処方に従つて調製した:
成 分 重量/重量%
ココアミドホスホベタイン 10.0
トリス―ステアリルアミドホスフエートエステ
ル 1.0
クエン酸ナトリウム 10.0
グリセリン 1.0
螢光増白剤 0.5
香 料 0.3
脱イオン水を加えて 100%
上のPHは15%HClで7.0±1に調整した。
実施例XIの組成物を、次の手順を用いて2つの
商業的に入手できる組成物で洗浄力について試験
する:
テスト・フアブリツクス社(Test Fabrics.
Jnc.)から入手した標準の汚れた羊毛布はくを用
いて、一定の組成物の相対的清浄能力を評価す
る。ターグーオートメーター(Terg―O―
Tometer)7243型を用いて清浄作用をシミユレ
ートする。制御した条件は次のとおりである:
1 洗たく時間(5分)
2 洗たく速度(100rpm)
3 水洗時間(5分)
4 水洗速度(100rpm)
5 洗たくおよび水洗の温度(105〓、40.6℃)
試験布を羊毛シヤリ織から作り、10ヤード
(9.14m)ロールにとする。主として油煙、油お
よび工業溶剤からなる汚れ混合物を、布に印刷ロ
ールで施こし、8インチ(20.32cm)幅の布の半
分のみが汚れるようにする。
この試験布を4×8インチ(10.16×20.32cm)
のストリツプに切つて、各ストリツプの半分が汚
れ、そして半分が汚れないようにする。ガードナ
ー色差計を用いて、各ストリツプの汚れた部分と
汚れない部分の両方について初期の色値(白色
度)を得る。これらのストリツプの3枚を3枚の
4×8インチ(10.16×20.32cm)の綿のフイラー
(filler)ストリツプと一緒に、1000mlの試験組成
物の10%水溶液を含有するターグーオートメータ
ーのビーカーに入れる。この前に、溶液を105〓
(40.6℃)で2分間かきまぜ、平衡にする。試料
を5分間かきまぜ、取り出し、絞り、そして105
〓(40.6℃)の1000mlの水道水を含有するかきま
ぜビーカーにもどす。5分間かきまぜた後、スト
リツプを取り出し、絞り、そして平らに置いて乾
燥する。乾燥したとき、それらを再び色差計で評
価して、汚れの除去された程度ならびに汚れが布
の汚さなかつた部分に付着した程度を決定する。
相対的清浄効果は、4Rとして特徴づけられる初
期と最終の白色度の測定値の間の広がりで示され
る。2単位の4Rは有意と考える。商用組成物を
実施例XIの組成物と比較し、次の結果を得た:
△R
商用組成物 5.7
商用組成物 8.0
実施例XIの組成物 8.4
実施例 XII
次の組成を有する注ぎかけ(pour―on)クリ
ームリンスを調製する:
重量/重量%
実施例のリン酸トリエステル 1.10
エチルジヒドロキシプロピルパラ―アミノ安息
香酸 0.55
ベンジルアルコール 0.55
ステアリルアルコール 0.88
イソステアリルアルコール 0.33
香 料 0.11
ヒドロキシエチルセルロース 0.83
水酸化ナトリウム 0.21
脱イオン水を加えて 100%
この組成物はきわめてすぐれた湿つた梳毛性質
およびコンデイシヨニング性質を示す。
実施例
本発明の新規な化合物の抗微生物性を明らかに
するため、次の標準の最小阻止濃度試験を行つ
て、種々の試験有機体の生育を阻止する最小有効
濃度を決定した。最初に、実施例およびの各
化合物の200mgを100mlの蒸留水に入れて2.00mg/
mlの濃度にし、次いで10系列の2倍希釈を行つて
0.0038mg/mlの最終濃度にする。こうして、
0.0038mg/ml〜2.00mg/mlの濃度の範囲を準備す
る。別に、1000mlの標準の抗生培地#3を各試験
微生物の24時間液体培地の培養物の1mlで接種
し、そして生ずる溶液を2mlの部分ずつ13mm×
100mmの試験管に4℃で入れる。各試験微生物に
ついて2本の試験管を準備する。
次いで、0.4mlの各濃度の被験化合物を各試験
管に入れ、それらを次に35℃で18時間振とう配置
する。活性の終点はトリプチケース大豆寒天培地
に対して目盛定めループ(loop)を用いて生育す
る最後の試験管(濃度)を決定するストリーキン
グ(streaking)により決定し、そして次の最大
濃度を最小阻止濃度とみなす。結果を下表に示
す:[Formula] is placed in a reactor, and while stirring vigorously, 1 part of concentrated phosphoric acid is added dropwise. The rate of addition of phosphoric acid is adjusted to maintain the reaction temperature between 65 and 95°C, preferably between 85 and 90°C. A halogen-containing epibiphosphate intermediate is produced. Three parts of the appropriate tertiary amine are added in portions while maintaining the reaction temperature between 90-100°C. After complete addition of amine, reduce the reaction mixture to 100-120
Heat to 0.degree. C. until argentometric titration of an aliquot indicates completion of the reaction. After cooling, the reaction mixture is dissolved in hot methanol/acetone. The desired product is obtained by isolating and drying the precipitate formed by cooling the methanol/acetone solution. The novel phosphotriester compound of the present invention is
It is a cationic surfactant and can be easily sorbed onto hair or other negatively charged surfaces to reduce electrostatic interactions. R 4 , R 5 or R 6 is 16
When hair has more carbon skeletons than carbon atoms, when such compounds are applied to hair, it causes the hair to “flow in the wind”.
is reduced and the combing in wet and dry conditions is very good. Generally, cationic quaternary ammonium salts are not readily compatible with a wide range of other surfactants. Surprisingly, the novel compounds of the present invention are compatible with a wide range of surfactants, such as anionic surfactants of the sodium lauryl sulfate type or sodium lauryl ether sulfate type; such as betaines, salteines and phosphobetaines. Amphoteric surfactants; readily compatible with nonionic surfactants such as ethoxylated sorbitan esters. Because of this unexpected compatibility, the compounds of the present invention can be easily incorporated into common shampoo and cream rinse formulations. The compounds of this invention can be used in amounts of about 0.1 to about 20% by weight, depending on the composition in which they are utilized. If more than 20% by weight is used, the resulting composition may have a poor texture and be irritating when used as a shampoo or cream rinse. Furthermore, in the formula (10 negative) of the novel phosphoric acid triester compound of the present invention, when A or R 5 which is a constituent part of A has a carbon chain length of 8 to 14 carbon atoms,
These compounds exhibit significant bacteriostatic and bactericidal properties. Compounds having these properties can be used at about 0.1% to about 5.0% by weight of the total composition. If amounts less than about 0.1% are used, the desired properties may be obtained, and if amounts greater than about 5.0% are used, the resulting compositions may be harsh to the touch and may be irritating. The following examples illustrate the invention. Example 500ml with overhead stirrer, water-cooled condenser, dropping funnel, thermometer and heating mantle
46.53 g of epichlorohydrin is placed in a glass reactor. 19.0 g of 85.5% phosphoric acid is then added via the addition funnel with vigorous stirring, adjusting the addition rate to maintain the temperature between 80-85°C. When the exothermic reaction ceases, the reactor is heated and the reaction mixture is maintained at 80°C for 1 hour. then
Add 148 g of octadecyldimethylamine to the reactor and stir the mixture for 20 hours at 102°C. Completion of the reaction is confirmed by argentometric titration of the chlorine ions generated. After cooling to approximately 40 °C, the reaction mixture was diluted with 200 ml of ethanol and transferred to a 2 volume beaker.
Add 1000ml of acetone. A yellow and colored precipitate forms, which is isolated by suction filtration and recrystallized from an ethanol/acetone mixture to give a yellow and colored powder. Silver titration for chloride ions and saponification assays show this material to be 98.6% pure. This product contains a novel phosphotriester of the following structural formula: Examples Using the glass reactor described in Examples,
93.52 g of epichlorohydrin is reacted with 38 g of 85.5% phosphoric acid at 85-90° C. for 2 hours. 213.2 g of dodecyldimethylamine are then added over a period of 3 hours, maintaining the temperature at 85-90°C.
Heating for a further 72 hours at 100±5° C. gives an argentometric titration value for chloride ions indicating greater than 90% completion of the reaction. The reaction product is isolated according to the procedure of the example, resulting in a pale yellow, colored, free-flowing powder that is assayed to be 99.0% pure. This product contains a triester of phosphoric acid with the following structure: EXAMPLE Using the apparatus described in the example, 19.0 g of concentrated phosphoric acid is added dropwise to 46.53 g of epichlorohydrin while maintaining the reaction temperature at 85-90°C. 176.5 g of a molten 50/50 mixture of eicosyldimethylamine and docosyldimethylamine was added to the temperature
Add over 2 hours while keeping at 100℃. 100℃
After another 12 hours at
The temperature rises to 140℃. After cooling, the desired product is isolated by crystallization from hot ethanol, filtering off with suction and drying. According to argentometric titration, the activity is 94.6%. The structure is identical to that of the example except that the C 12 H 25 substituent is replaced with a mixed group of C 20 H 41 and C 22 H 45 in a 1:1 ratio. EXAMPLE Using two glass reactors equipped with an overhead stirrer and a reflux condenser, 140.28 g of epichlorohydrin is reacted with 57 g of 85.5% phosphoric acid and the reaction is stirred for 2 hours at 85-90°C. To this reaction product, 548.6 g of 3-oleamidopropyl dimethylamine was added and the temperature was increased to 95-95.
The temperature rises to 100℃. After 22 hours, argentometric titration shows that the reaction is nearing completion and the reaction mixture is cooled. After crystallization from ethanol/acetone, suction filtration and drying, a gray powder is obtained. This product contains a novel phosphotriester of the following structure: Example Using the reactor and reaction conditions described in the example,
112.2 g of epichlorohydrin is reacted with 45.6 g of 85.5% phosphoric acid. Then, 458.4 g of stearamide ethyl diethylamine is added to the reaction mixture and the reaction mixture is maintained at 95° C. for 20 hours. Completion of the reaction is estimated by argentometric titration and the reaction product contains a novel phosphotriester of the following structure: Example 297 g of octadecyldimethylamine and 80 g of ethylene chlorohydrin are dissolved in absolute ethanol to a total volume of 1500 ml. The mixture is then heated in a 2 volume round bottom flask equipped with a reflux condenser. After 6 days, titration of chloride ions shows that the reaction is 91% complete and the reaction is stopped. The desired stearyldimethyl-2-hydroxyethylammonium chloride is isolated by precipitation with acetone. After recrystallization from an ethanol/acetone mixture, filtration and drying under vacuum, a white powder is obtained which, when titrated for chloride ions, is determined to be 98.9% pure. 228.7 g of this steryl dimethyl-2-hydroxyethylammonium chloride is then placed in a 2 volume three-neck round bottom flask equipped with an overhead stirrer, addition funnel, and reflux condenser.
Add 1200 ml of methylene chloride and disperse the quaternary ammonium compound with vigorous stirring. 30.70
g of phosphorus oxychloride, POCl 3 , are added dropwise over 1 hour. The reaction mixture is then refluxed for 18 hours, the methylene chloride is removed by distillation and the triester is purified by recrystallization from hot acetone. This product contains a novel phosphotriester of the following structure: Example 213.14 g of dodecyldimethylamine are dissolved in 1200 ml of absolute ethanol, 80 g of ethylene chlorohydrin are added and the resulting reaction mixture is stirred for 72 hours. Dodecyldimethyl-2-hydroxyethylammonium chloride is obtained in a yield of 84% after precipitation with acetone, recrystallization with ethanol/acetone, filtration and drying in vacuo. 175.9
g of dodecyldimethyl-2-hydroxyethylammonium chloride is reacted with 30.70 g of phosphorus oxychloride using the equipment and reaction conditions described in the Examples. This product contains a novel phosphotriester of the following structure: Example 305.6 g of stearamide ethyl diethylamine are dissolved in 2000 ml of absolute ethanol. then 64
g of ethylene chlorohydrin are added and the reaction mixture is refluxed for 120 hours. Approximately three quarters of the ethanol is then removed by flash evaporation, acetone is added at the boiling point to saturation and the reaction mixture is cooled to room temperature. The white precipitate that forms is isolated, dried in vacuo, and identified as stearamide ethyl diethyl-2-hydroxyethylammonium chloride. 277.2g of this stearamide ethyl diethyl
2-hydroxyethylammonium chloride
React with 30.7 g of phosphorus oxychloride using the equipment and reaction conditions described in the Examples. This product contains a novel phosphotriester with the following structure: EXAMPLE A hair care product is prepared as follows: Structure: 150 parts by weight of a 30% active solution of phosphobetaine, where R is a C 11 -C 13 mixed group in a ratio of 1:1,
Add 200 parts of distilled water at ambient temperature followed by 77 parts by weight of a 26% active solution of the cationic triphosphate ester of the example and mix the resulting solution until clear and homogeneous. It is then prepared by the method described in U.S. Pat. No. 2,970,160 and has the following formula: 150 parts by weight of a 30% active solution of an amphoteric substance of the formula are added, where R is a C 11 -C 13 mixed group in a ratio of 1:1. Then 200 parts of 72% polyoxyethylene (80) sorbitan monococoate are added, followed by 12 g of polyethylene glycol 6000 distearate and the resulting mixture is stirred at 70° C. for 20 minutes. The solution is cooled to 35°C and the pH is adjusted to 7.0±1 with 15% HCl solution. Add preservatives and fragrances
Add enough deionized water to bring the total to 1000 g. The final product is transparent and tested at 12 rpm using a #2 spindle on a Bruckfield viscometer at 25°C.
The viscosity measured at is 1225 cps. This product exhibits excellent foaming and cleaning properties,
Beauty Salon's half head
head) Shows conditioning effects on hair as confirmed by research. These studies involved separating each subject's hair into two sections, treating one section with a shampoo composition containing the novel compound of the invention, and treating the other section with the same composition without the novel compound. and grade the results subjectively according to the same guidelines. EXAMPLES The following detergent hair or skin cleansers are prepared according to the procedure outlined in the examples: Ingredients W/W % Cocoamidopropyl sultamine 5.00 Tridecyl ether(4) sulfate 5.00 Tris-stearylaminophosphate Ester 0.30 Propylene Glycol 1.00 Thickener 2.00 Preservative 0.10 Dye 0.02 Fragrance 0.20 Add deionized water to 100% Above pH was adjusted to 5.5 with dilute HCl. Examples Whitening agent 0.5 Fragrance 0.3 Deionized water was added to 100%.The pH above was adjusted to 7.0±1 with 15% HCl. The composition of Example XI is tested for cleaning power with two commercially available compositions using the following procedure: Test Fabrics.
The relative cleaning ability of certain compositions is evaluated using standard soiled woolen fabric foils obtained from Jnc. Terg-O-
Tometer) Model 7243 is used to simulate the cleaning action. The controlled conditions are as follows: 1 Washing time (5 minutes) 2 Washing speed (100 rpm) 3 Washing time (5 minutes) 4 Washing speed (100 rpm) 5 Washing and washing temperature (105〓, 40.6°C) Test The cloth is made from wool shari weave and rolled into 10 yard (9.14 m) rolls. A stain mixture consisting primarily of soot, oil and industrial solvents is applied to the fabric with a print roll so that only half of the 8 inch wide fabric is stained. This test cloth is 4 x 8 inches (10.16 x 20.32 cm)
Cut into strips so that half of each strip is soiled and half is clean. A Gardner colorimeter is used to obtain initial color values (whiteness) for both the soiled and clean portions of each strip. Three of these strips, along with three 4 x 8 inch (10.16 x 20.32 cm) cotton filler strips, were placed in a Targu Autometer beaker containing 1000 ml of a 10% aqueous solution of the test composition. Put it in. Before this, add the solution to 105%
Stir at (40.6℃) for 2 minutes to equilibrate. Stir the sample for 5 minutes, remove, squeeze, and
〓Return to stirred beaker containing 1000ml of tap water at (40.6℃). After stirring for 5 minutes, remove the strips, squeeze, and lay flat to dry. When dry, they are evaluated again with a colorimeter to determine the extent to which the stain has been removed as well as the extent to which the stain has adhered to the unsoiled areas of the fabric.
The relative cleaning effect is indicated by the spread between the initial and final whiteness measurements, characterized as 4R. We consider 2 units of 4R to be significant. The commercial composition was compared with the composition of Example XI and the following results were obtained: △R Commercial Composition 5.7 Commercial Composition 8.0 Composition of Example XI 8.4 Example -on) Prepare cream rinse: W/W % Phosphate triester of example 1.10 Ethyl dihydroxypropyl para-aminobenzoic acid 0.55 Benzyl alcohol 0.55 Stearyl alcohol 0.88 Isostearyl alcohol 0.33 Fragrance 0.11 Hydroxyethyl cellulose 0.83 Sodium hydroxide 0.21 100% with deionized water This composition exhibits excellent wet carding and conditioning properties. EXAMPLES To demonstrate the antimicrobial properties of the novel compounds of the present invention, the following standard minimum inhibitory concentration test was conducted to determine the minimum effective concentration that inhibits the growth of various test organisms. First, add 200 mg of each compound of Examples and 2.0 mg/kg to 100 ml of distilled water.
ml, then make 10 series of 2-fold dilutions.
Make a final concentration of 0.0038 mg/ml. thus,
Prepare a concentration range of 0.0038 mg/ml to 2.00 mg/ml. Separately, 1000 ml of standard antibiotic medium #3 was inoculated with 1 ml of a 24-hour broth culture of each test organism, and the resulting solution was divided into 2 ml portions 13 mm x
Place in a 100 mm test tube at 4°C. Prepare two test tubes for each test organism. 0.4 ml of each concentration of test compound is then placed in each test tube and they are then placed shaking at 35° C. for 18 hours. The end point of activity is determined by streaking using a graduated loop on trypticase soy agar to determine the last tube (concentration) to grow, and then the next maximum concentration to the minimum inhibition. Considered as concentration. The results are shown in the table below:
【表】
これらの結果は、対照の制菌剤および/または
殺菌剤、たとえば、塩化セチルピリジニウムと比
較すると、本発明の新規な化合物が比較的低い濃
度で制菌性および殺菌性を示し、そしてすぐれた
抗微生物剤であることを明らかにする。
本発明をある好ましい態様について説明しかつ
例示したが、種々の変更、変化、省略および置換
を本発明の精神を逸脱しないで当業者はなすこと
ができるであろう。したがつて、本発明は特許請
求の範囲によつてのみ限定される。TABLE These results demonstrate that the novel compounds of the present invention exhibit bactericidal and bactericidal properties at relatively low concentrations when compared to reference bacteriostatic and/or bactericidal agents, such as cetylpyridinium chloride, and It is revealed that it is an excellent antimicrobial agent. Although the invention has been described and illustrated with respect to certain preferred embodiments, various modifications, changes, omissions and substitutions may be made by those skilled in the art without departing from the spirit of the invention. Accordingly, the invention is limited only by the scope of the claims.
Claims (1)
ルキレンであり、 R2とR3が低級アルキルであり、そして Aが直鎖または分岐C12―22アルキルまたは式
―R4―NHCO―R5で表わされ、式中、 R4が低級アルキレンであり R5がC12―22アルキルである 基であり、 Xがハロゲンである 化合物。 2 特許請求の範囲第1項記載の化合物であつて
XがClまたはBrである化合物。 3 特許請求の範囲第1項記載の化合物であつ
て、式 の化合物。 4 特許請求の範囲第1項記載の化合物であつ
て、式 の化合物。 5 特許請求の範囲第1項記載の化合物であつ
て、式 式中RaがC20H41およびC22H45の1:1の比の
混合基である、 の化合物。 6 特許請求の範囲第1項記載の化合物であつ
て、式 の化合物。 7 特許請求の範囲第1項記載の化合物であつ
て、式 の化合物。 8 特許請求の範囲第1項記載の化合物であつ
て、式 の化合物。 9 特許請求の範囲第1項記載の化合物であつ
て、式 の化合物。 10 特許請求の範囲第1項記載の化合物であつ
て、式 の化合物。 11 式 で表わされ、式中、 R1が低級アルキレンまたはヒドロキシ低級ア
ルキレンであり、 R2とR3が低級アルキルであり、そして Aが直鎖または分岐C12―22アルキルまたは式
―R4―NHCO―R5で表わされ、式中、 R4が低級アルキレンであり R5がC12―22アルキルである 基であり、 Xがハロゲンである 化合物の製造方法であつて、 a 一般式NR2R3―A(R2,R3,Aは上記の通
り)で表わされる第三アミンをX―R1―OH
(X,R1は上記の通り)で表わされる化合物で
第四級化してヒドロキシル基含有第四級アンモ
ニウム化合物を生成し、 そして b このヒドロキシル基含有第四級アンモニウム
化合物をオキシハロゲン化リンと反応させる ことからなる方法。 12 式 で表わされ、式中、 R1が【式】であり、 R2とR3が低級アルキルであり、そして Aが直鎖または分岐C12―22アルキルまたは式
―R4―NHCO―R5で表わされ、式中、 R4が低級アルキレンであり R5がC12―22アルキルである 基であり、 Xがハロゲンである 化合物の製造方法であつて、 a 一般式【式】(Xは上記の通 り、Yは低級アリキレン)で表わされるエピハ
ロヒドロリンをリン酸と反応させてハロゲン含
有エピハロヒドリンフオスフエート中間体を生
成し、 そして b このハロゲン含有エピハロヒドリンフオスフ
エート中間体を一般式NR2R3―A(R2,R3,A
は上記の通り)で表わされる化合物と反応させ
ることからなる方法。[Claims] 1 formula represented by the formula, R 1 is lower alkylene or hydroxy lower alkylene, R 2 and R 3 are lower alkyl, and A is straight chain or branched C 12 - 22 alkyl or the formula -R 4 -NHCO -A compound represented by R5 , in which R4 is lower alkylene , R5 is C12-22 alkyl, and X is halogen. 2. A compound according to claim 1, wherein X is Cl or Br. 3. A compound according to claim 1, which has the formula compound. 4. A compound according to claim 1, which has the formula compound. 5. A compound according to claim 1, which has the formula A compound of the formula wherein Ra is a mixed group of C20H41 and C22H45 in a ratio of 1:1. 6. A compound according to claim 1, which has the formula compound. 7. A compound according to claim 1, which has the formula compound. 8. A compound according to claim 1, which has the formula compound. 9 A compound according to claim 1, which has the formula compound. 10 A compound according to claim 1, which has the formula compound. 11 formula represented by the formula, R 1 is lower alkylene or hydroxy lower alkylene, R 2 and R 3 are lower alkyl, and A is straight chain or branched C 12 - 22 alkyl or the formula -R 4 -NHCO - A method for producing a compound represented by R 5 , in which R 4 is lower alkylene, R 5 is C 12 - 22 alkyl, and X is halogen, the compound having the general formula NR 2 A tertiary amine represented by R 3 —A (R 2 , R 3 , A are as above) is replaced by X—R 1 —OH
(X, R 1 are as above) to produce a hydroxyl group-containing quaternary ammonium compound, and b react this hydroxyl group-containing quaternary ammonium compound with phosphorus oxyhalide. A method consisting of letting. 12 formula In the formula, R 1 is [Formula], R 2 and R 3 are lower alkyl, and A is a straight chain or branched C 12 - 22 alkyl or the formula -R 4 -NHCO-R 5 A method for producing a compound represented by the general formula [ Formula ] (X As described above, an epihalohydroline represented by Y (lower alikylene) is reacted with phosphoric acid to produce a halogen-containing epihalohydrin phosphate intermediate, and b this halogen-containing epihalohydrin phosphate intermediate has the general formula NR 2 R 3 -A (R 2 , R 3 , A
is as described above).
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US5983879A | 1979-07-23 | 1979-07-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5622791A JPS5622791A (en) | 1981-03-03 |
JPS648634B2 true JPS648634B2 (en) | 1989-02-14 |
Family
ID=22025612
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9944980A Granted JPS5622791A (en) | 1979-07-23 | 1980-07-22 | Phosphoric acid triester |
Country Status (18)
Country | Link |
---|---|
JP (1) | JPS5622791A (en) |
KR (1) | KR850000076B1 (en) |
AR (1) | AR228431A1 (en) |
AU (1) | AU536481B2 (en) |
BR (1) | BR8004564A (en) |
CA (1) | CA1126750A (en) |
DE (1) | DE3027943A1 (en) |
ES (1) | ES8105740A1 (en) |
FR (1) | FR2461715A1 (en) |
GR (1) | GR70013B (en) |
IN (1) | IN153525B (en) |
IT (1) | IT8049277A0 (en) |
MX (1) | MX5854E (en) |
NZ (1) | NZ194289A (en) |
PH (1) | PH17453A (en) |
PT (1) | PT71585B (en) |
ZA (1) | ZA804419B (en) |
ZW (1) | ZW16980A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3326230A1 (en) * | 1983-07-21 | 1985-01-31 | Henkel KGaA, 4000 Düsseldorf | AGENT FOR WASHING AND RINSING HAIR |
DE3409634A1 (en) * | 1984-03-16 | 1985-09-19 | Henkel KGaA, 4000 Düsseldorf | PHOSPHONIC ACID ESTERS IN HAIR TREATMENT AGENTS |
JPS6122096A (en) * | 1984-07-09 | 1986-01-30 | Kao Corp | Saccharide phosphoric ester and its preparation |
US5300494A (en) * | 1986-06-06 | 1994-04-05 | Union Carbide Chemicals & Plastics Technology Corporation | Delivery systems for quaternary and related compounds |
ATE196592T1 (en) * | 1991-10-28 | 2000-10-15 | Dennis L Fost | PHOSPHOLIPIDE ANTIMICROBIAL COMPOSITIONS |
FR2725365B1 (en) * | 1994-10-07 | 1996-11-08 | Oreal | CLEANSING AND / OR MAKE-UP REMOVAL COMPOSITION CONTAINING AN ALCOHOL AND A PHOSPHATE COMPOUND |
US5567427A (en) * | 1995-03-17 | 1996-10-22 | Helene Curtis, Inc. | Emulsified, low ph cosmetic compositions having improved stability |
CN105968133B (en) * | 2016-05-18 | 2018-09-21 | 大连和田科技有限公司 | A kind of preparation method of phosphate quaternary ammonium salt bactericide |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4181634A (en) * | 1977-06-17 | 1980-01-01 | Johnson & Johnson | Mild cleansing compositions comprising an alkyleneoxylated bisquaternary ammonium compound and an anionic or amphoteric detergent such as a phosphobetaine |
AR228016A1 (en) * | 1978-05-05 | 1983-01-14 | Johnson & Johnson | COMPOSITE OF THE GROUP OF PHOSPHOBETINES AND PHOSPHYTAINS, USEFUL AS ANPHOTERIC AND ZWITTERIONIC SURFACTANT |
EP0013713B1 (en) * | 1978-11-30 | 1984-04-11 | Mona Industries | Phosphorus containing surface active agents and their preparation |
US4209449A (en) * | 1978-11-30 | 1980-06-24 | Mona Industries | Phosphate quaternary compounds |
-
1980
- 1980-06-30 AU AU59762/80A patent/AU536481B2/en not_active Expired
- 1980-07-05 IN IN783/CAL/80A patent/IN153525B/en unknown
- 1980-07-09 NZ NZ194289A patent/NZ194289A/en unknown
- 1980-07-14 KR KR1019800002803A patent/KR850000076B1/en active
- 1980-07-16 FR FR8015682A patent/FR2461715A1/en active Pending
- 1980-07-17 GR GR62484A patent/GR70013B/el unknown
- 1980-07-18 IT IT8049277A patent/IT8049277A0/en unknown
- 1980-07-21 CA CA356,655A patent/CA1126750A/en not_active Expired
- 1980-07-21 PT PT71585A patent/PT71585B/en unknown
- 1980-07-22 JP JP9944980A patent/JPS5622791A/en active Granted
- 1980-07-22 PH PH24323A patent/PH17453A/en unknown
- 1980-07-22 ES ES493597A patent/ES8105740A1/en not_active Expired
- 1980-07-22 ZA ZA00804419A patent/ZA804419B/en unknown
- 1980-07-22 BR BR8004564A patent/BR8004564A/en not_active IP Right Cessation
- 1980-07-22 AR AR281844A patent/AR228431A1/en active
- 1980-07-22 ZW ZW169/80A patent/ZW16980A1/en unknown
- 1980-07-23 MX MX808930U patent/MX5854E/en unknown
- 1980-07-23 DE DE19803027943 patent/DE3027943A1/en active Granted
Also Published As
Publication number | Publication date |
---|---|
IN153525B (en) | 1984-07-21 |
KR850000076B1 (en) | 1985-02-18 |
AU536481B2 (en) | 1984-05-10 |
MX5854E (en) | 1984-08-09 |
ES493597A0 (en) | 1981-06-16 |
KR830003506A (en) | 1983-06-21 |
CA1126750A (en) | 1982-06-29 |
GR70013B (en) | 1982-07-23 |
PT71585A (en) | 1980-09-01 |
DE3027943A1 (en) | 1981-02-19 |
PT71585B (en) | 1981-12-17 |
JPS5622791A (en) | 1981-03-03 |
PH17453A (en) | 1984-08-29 |
ZA804419B (en) | 1982-02-24 |
DE3027943C2 (en) | 1988-09-01 |
ES8105740A1 (en) | 1981-06-16 |
AU5976280A (en) | 1981-01-29 |
NZ194289A (en) | 1982-09-07 |
FR2461715A1 (en) | 1981-02-06 |
ZW16980A1 (en) | 1982-04-21 |
BR8004564A (en) | 1981-02-03 |
AR228431A1 (en) | 1983-03-15 |
IT8049277A0 (en) | 1980-07-18 |
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