GB709482A - Polyethylene glycol derivatives and method of making same - Google Patents

Polyethylene glycol derivatives and method of making same

Info

Publication number
GB709482A
GB709482A GB13296/51A GB1329651A GB709482A GB 709482 A GB709482 A GB 709482A GB 13296/51 A GB13296/51 A GB 13296/51A GB 1329651 A GB1329651 A GB 1329651A GB 709482 A GB709482 A GB 709482A
Authority
GB
United Kingdom
Prior art keywords
polyethylene glycol
acid
ester
molecular weight
formula
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
Application number
GB13296/51A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ciba AG filed Critical Ciba AG
Publication of GB709482A publication Critical patent/GB709482A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention comprises compounds of the general formula RO(CH2CH2O)nCH2 CH2. ZCOOH- in which R stands for an alkyl, cycloalkyl, aryl or aralkyl radical containing at most 7 carbon atoms, n for an integer from 6 to 50 p inclusive and Z for one of the groupings -CH2-, <FORM:0709482/IV (a)/1> , -S.CH2-, and -O. arylene-and Y is an alkyl group containing at most 7 carbon atoms. Such compounds are obtained by condensing a reactive ester of the formula CH2(COOY)2, CH3COCH2COOY, NHY.CN2COOY, HS.CH2.COOY, HO.Ar. COOY (where Ar is arylene) or CN.CH2. COOY (where Y is an alkyl radical containing at most 7 carbon atoms) with a polyethylene glycol derivative of a formula RO(CH2CH2O)n CH2CH2X where X is halogen or the residue of a strong, monobasic organic acid (e.g. as prepared in Specification 709,478) followed by hydrolysis of the ester produced to the free acid and (where the resulting product is an a - substituted malonic acid) by the splitting off of carbon dioxide to give the monocarboxylic acid. The products are of use in medicines. In an example (1) p-hydroxy methyl benzoate is reacted in the presence of sodium methoxide with the bromide of a polyethylene glycol monomethyl ether of average weight 414. The product of formula CH3O(CH2CH2O)n CH2CH2O-pC6H4 .COOCH3 (average value of n is about 6) is hydrolysed to the free acid. Salicylic ester, isopropyl 2-hydroxy-5-methyl benzoate or methyl 4-hydroxy -1- naphthoate may be used in place of the methyl p-hydroxybenzoate. In a similar manner there are produced (2) from polyethylene glycol monoisopropyl ether (molecular weight 900), the compound of the formula iso- C3H7O (Ch2 CH2O) nCH2CH2O-p-C6H4 .COOC4H9 (n has average value 15), which is hydrolysed to the free acid. As starting material may be used instead the p-toluene sulphonic acid ester of polyethylene glycol monobenzyl ether (molecular weight 2000); (3) from diisopropylmalonate and the p-toluene sulphonic acid ester of polyethylene glycol monophenyl ether (molecular weight 650), a compound C6H5O <FORM:0709482/IV (a)/2> is produced, which is hydrolysed to the dicarboxylic acid and the latter is decarboxylated to the monocarboxylic acid (n is about 8). Analagously the benzene sulphonic acid ester of polyethylene glycol monocyclopentyl ether (molecular weight 500) is employed; (4) from thioglycolic acid ethyl ester and the benzene or methane sulphonic acid ester of polyethylene glycol monomethyl ether (molecular weight 690 or 628) a thioether of formula CH3O <FORM:0709482/IV (a)/3> is obtained (n is about 11) which is saponified to the free acid; (5) from sarcosine ethylester and the iodide or benzene sulphonate of polyethylene glycol monomethyl ether (molecular weight 690) an ester of formula <FORM:0709482/IV (a)/4> is obtained and is hydrolysed to the free acid (n being about 11). The acid products of (2) and (4) may be recovered by absorption on a basic exchange resin and elution therefrom.ALSO:The invention comprises compounds of the general formula RO(CH2CH2O)nCH2CH2.Z.COOH in which R stands for an alkyl, cycloalkyl, aryl or aralkyl radical containing at most 7 carbon atoms, n for an integer from 6 to 50 inclusive, and Z for one of the groupings -CH2-, <FORM:0709482/IV (b)/1> -S.CH2-, and -O-arylene-, and Y is an alkyl group containing at most 7 carbon atoms. Such compounds are obtained by condensing a reactive ester of the formula CH2(COOY)2, CH3COCH2COOY, NHY.CH2.COOY, HS.CH2.COOY, HO . Ar . COOY (where Ar is arylene), or CN . CH2 . COOY (where Y is an alkyl radical containing at most 7 carbon atoms), with a polyethylene glycol derivative of formula RO(CH2CH2O)nCH2CH2X, where X is halogen or the residue of a strong, monobasic organic acid (e.g. as prepared in Specification 709,478), followed by hydrolysis of the ester produced to the free acid and (where the resulting product is an a -substituted malonic acid) by the splitting off of carbon dioxide to give the monocarboxylic acid. The products are of use in medicines. In an example: (1) p-hydroxy methyl benzoate is reacted in presence of sodium methoxide with the bromide of a polyethylene glycol monomethyl ether of average molecular weight of 414. The product, of formula CH3O(CH2CH2O)nCH2CH2O . pC6H4 . COOCH3 is hydrolysed to the free acid (n is about 6). Salicylic ester, isopropyl 2-hydroxy-5-methyl benzoate or methyl-4-hydroxy-1-naphthoate may replace the methyl p-hydroxybenzoate. In a similar manner are obtained (2) from polyethylene glycol mono-isopropyl ether (molecular weight 900), the compound iso-C3H7O(CH2 <FORM:0709482/IV (b)/2> , which is hydrolysed to the free acid (n is about 15). As starting material may be used instead the p-toluene sulphonic acid ester of polyethylene glycol monobenzyl ether (molecular weight 2000); (3) from diiscpropylmalonate and the p-toluene sulphonic acid ester of polyethylene glycol monophenyl ether (molecular weight 650), a compound <FORM:0709482/IV (b)/3> is produced which is hydrolysed to the dicarboxylic acid and the latter is decarboxylated to the monocarboxylic acid (n is about 8). Analogously, ethyl aceto-acetate is alkylated with polyethylene glycol monocyclopentyl ether and the product is saponified; (4) from thioglycolic acid ethyl ester and the benzene sulphonic acid ester of polyethylene glycol mono-methyl ether (molecular weight 690) or the methane sulphonic acid ester of polyethylene glycol monomethyl ether (molecular weight 628), a thioether CH3O(CH2CH2O)n . CH2CH2S . CH2COOC2H5 is obtained which is hydrolysed to the acid (n is about 11); (5) from sarcosine ethyl ester and polyethylene glycol monomethyl ether benzene sulphonate or iodide, an ester of formula <FORM:0709482/IV (b)/4> is obtained and is hydrolysed to the free acid (n having an average value of about 11). The acid products of (2) and (4) may be recovered by adsorption on a basic exchange resin and elution therefrom.
GB13296/51A 1950-06-06 1951-06-05 Polyethylene glycol derivatives and method of making same Expired GB709482A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH709482X 1950-06-06

Publications (1)

Publication Number Publication Date
GB709482A true GB709482A (en) 1954-05-26

Family

ID=4530652

Family Applications (1)

Application Number Title Priority Date Filing Date
GB13296/51A Expired GB709482A (en) 1950-06-06 1951-06-05 Polyethylene glycol derivatives and method of making same

Country Status (1)

Country Link
GB (1) GB709482A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2148910A (en) * 1983-10-28 1985-06-05 Chevron Res Stable emulsifier for substituted succinic anhydride compositions
CN109942803A (en) * 2017-12-21 2019-06-28 江苏美思德化学股份有限公司 A kind of esterification end-capping allyl polyethers and preparation method thereof
CN113234220A (en) * 2021-05-19 2021-08-10 浙江海洋大学 Flower-shaped structure Fe for photodegradation of ciprofloxacin3O4/Bi2WO6Process for preparing catalyst

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2148910A (en) * 1983-10-28 1985-06-05 Chevron Res Stable emulsifier for substituted succinic anhydride compositions
CN109942803A (en) * 2017-12-21 2019-06-28 江苏美思德化学股份有限公司 A kind of esterification end-capping allyl polyethers and preparation method thereof
CN109942803B (en) * 2017-12-21 2021-04-06 江苏美思德化学股份有限公司 Esterified capped allyl polyether and preparation method thereof
CN113234220A (en) * 2021-05-19 2021-08-10 浙江海洋大学 Flower-shaped structure Fe for photodegradation of ciprofloxacin3O4/Bi2WO6Process for preparing catalyst

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