(19) *EP002851362B1* (11) EP 2 851 362 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 303/24 (2006.01) C07C 303/28 (2006.01) (2006.01) (2006.01) 27.11.2019 Bulletin 2019/48 C07C 305/06 C07C 305/08 C07C 305/20 (2006.01) C07C 305/24 (2006.01) (2006.01) (21) Application number: 13185032.3 C07C 309/73 (22) Date of filing: 18.09.2013 (54) A method for the production of sulfate or sulfonate esters Verfahren zur Herstellung von Sulfat oder Sulfonatestern Procédé pour la production d’esters de sulfate ou de sulfonate (84) Designated Contracting States: (56) References cited: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • DENIZ GUNES ET AL: "ALIPHATIC THIOETHERS GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO BY S-ALKYLATION OF THIOLS VIA TRIALKYL PL PT RO RS SE SI SK SM TR BORATES", PHOSPHORUS, SULFUR AND SILICON AND THE RELATED ELEMENTS, (43) Date of publication of application: TAYLOR & FRANCIS INC, US, vol. 185, no. 8, 1 25.03.2015 Bulletin 2015/13 January 2010 (2010-01-01), pages 1685-1690, XP008165903, ISSN: 1042-6507, DOI: (73) Proprietor: Ulusal Bor Arastirma Enstitusu 10.1080/10426500903213563 [retrieved on 06520 Ankara (TR) 2010-08-02] • OKI ET AL: "Solvothermal synthesis of carbon (72) Inventors: nanotube-B2O3 nanocomposite using tributyl • Bicak, Niyazi borate as boron oxide source", INORGANIC 34469 Istanbul (TR) CHEMISTRY COMMUNICATIONS, ELSEVIER, • Gunes, Deniz AMSTERDAM, NL, vol. 11, no. 3, 31 December 34744 Bostanci 2007 (2007-12-31), pages 275-278, XP022499511, Istanbul (TR) ISSN: 1387-7003, DOI: • Akbas, Cem Emre 10.1016/J.INOCHE.2007.12.015 Bahcelievler • ITAMAR M MALKOWSKY ET AL: "Facile and Istanbul (TR) Reliable Synthesis of Tetraphenoxybor ates and • Sirkecioglu, Okan Their Properties", EUROPEAN JOURNAL OF 34469 Sariyer INORGANIC CHEMISTRY, WILEY-VCH VERLAG, Istanbul (TR) WEINHEIM, DE, vol. 2006, no. 8, 1 March 2006 (2006-03-01), pages 1690-1697, XP008160248, (74) Representative: Dericioglu Kurt, Ekin ISSN: 1434-1948, DOI: 10.1002/EJIC.200600074 Ankara Patent Bureau Limited • ANDREI Y. BOCHKOV ET AL: "Synthesis of Kavaklidere Mahallesi 3-(5-Methylthiophen-2-yl)coumarins and Their Bestekar Caddesi No: 10 Photochromic Dihetarylethene Derivatives", 06680 Cankaya, Ankara (TR) JOURNAL OF HETEROCYCLIC CHEMISTRY, vol. 50, no. 4, 2 July 2013 (2013-07-02), pages 891-898, XP055089480, ISSN: 0022-152X, DOI: 10.1002/jhet.931 Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 851 362 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 851 362 B1 • Alex C. Bissember ET AL: "A Mild, • Ko Yasumoto: "Isolation of new aliphatic sulfates Palladium-Catalyzed Method for the and sulfamates as the Daphnia Kairomones Dehydrohalogenation of Alkyl Bromides: inducing morphological change of a Synthetic and Mechanistic Studies", Journal of phytoplankton Scenedesmus gutwinskii", Chem. the American Chemical Society, vol. 134, no. 34, Pharm. Bull., 1 January 2008 (2008-01-01), pages 20 August 2012 (2012-08-20), pages 14232-14237, 133-136, XP055494545, Retrieved from the XP055493627, US ISSN: 0002-7863, DOI: Internet: 10.1021/ja306323x URL:https://www.jstage.jst.go.jp/article/c • Alex C. Bissember ET AL: "A Mild, pb/56/1/56_1_133/_pdf/-char/en [retrieved on Palladium-Catalyzed Method for the 2018-07-23] Dehydrohalogenation of Alkyl Bromides: Synthetic and Mechanistic Studies - Supporting information", Journal of the American Chemical Society, vol. 134, no. 34, 29 August 2012 (2012-08-29), pages 14232-14237, XP055493629, US ISSN: 0002-7863, DOI: 10.1021/ja306323x • DREGER E E ET AL: "SODIUM ALCOHOL SULFATES PROPERTIES INVOLVING SURFACE ACTIVITY", INDUSTRIAL AND ENGINEERING CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 36, no. 7, 1 January 1944 (1944-01-01), pages 610-617, XP001041414, DOI: 10.1021/IE50415A004 2 EP 2 851 362 B1 Description Field of the Invention 5 [0001] The present invention relates to a method for the production of sulfate or sulfonate esters based on the acidolysis of the boron esters acquired from alcohol and boric acid with sulfuric acid or sulfonic acid. Background of the Invention 10 [0002] Sulfate and sulfuric acid esters known as well alkylating agents are used in alkylation of various compounds such as amines, carboxylic acids, alcohol and thiol. Today, alkylating reactions with these compounds are the subject of many researches. [0003] Sodium and potassium salts of sulfuric acid monoesters of long chain alcohols have extensive use in detergent formulations as surface active compounds. Recent searches have shown that sulfate monoesters are part of a number 15 of biological processes such as hormone regulation and molecular recognition. [0004] In order to prepare dialkyl sulfates, methods wherein the alcohols are reacted with tertiary amine-sulfur trioxide complexes are used. Dimethyl sulfate is obtained with the reaction based on direction interaction of sulfuric acid with methanol in high yields. However the said method causes low yields when the other alcohols are used. Yielding a number of by products such as alkene, isoalkene, ether and sulfate ester isomers after the reaction causes this situation. 20 [0005] Besides, industrial or laboratory scale production of alkyl sulfates seems to be confined to the use of tertiary amine- SO3 complexes. International Patent document no WO03020735, an application known in the state of the art, discloses alkylation of saccharides with pyridine-SO3 complex in dimethyl formamide (DMF) or dimethyl sulfoxide (DM- SO). [0006] International Patent document no WO9100852, another application known in the state of the art, discloses a 25 preparative method for large-scale production of trialkylamine-SO3 complex by reaction of chlorosulfonic acid with tertiary amines and their use in preparing alkyl sulfates. [0007] As it can be understood from the said documents, early studies realized for sulfation and sulfonation are limited to SO3 and its complexes. Furthermore, using sulfur dioxide (SO3) and its complexes which is highly corrosive and humectant by its nature requires special precautions. 30 [0008] European Patent document no EP1997869, another application known in the state of the art, discloses acquiring borated earth alkaline metal sulfonates with reaction of compounds including boric acid and boric acid anhydride or similar boron compounds with alcohols. In the said process, it is disclosed that materials involving boron such as boric acid, boron anhydride, boron ester and the like can be used as boron source. Borated sulfonic acid is used as starting material. 35 [0009] United States Patent document no US8269038 discloses esterification of sulfonic acids by reaction with low molecular weight dialkyl sulfates in the presence of pyridine in aprotic solvents such as dichloromethane. In another variant of this process, alkyl sulfonates are produced by reaction of alkyl iodides with sulfonic acids using pyridine as acid scavenger. [0010] United States Patent document no US7977525 discloses a process for separating olefins from n-alkanes or 40 their mixtures with iso-alkanes by forming sulfate esters. In this process n-alkanes in upper organic phase can be separated easily from aqueous sulfuric acid phase, but isolation and purification of the sulfate ester has not been described. Obviously the procedure given in this patent has been targeted mainly to remove alkenes from alkane-alkene mixtures. [0011] United States Patent document no US7863479, another application known in the state of the art, discloses 45 sulfation of alcoxylated alcohols by direct action of chlorosulfonic acid or sulfur trioxide complex The resulting monosulfate ester of this process is then neutralized with alkaline hydroxides or amines to give are laundry detergents. [0012] In a related patent, EP 1354872 A1, a process is described for synthesis of tertiary amine salts of sulfate monoesters. The amine components having amide, ester or carbonate units have been claimed to provide softening action in washing formulations. The patent, WO 00/58428 discloses heat-activatable cleaning formulation comprising 50 ethoxylated alkyl ether sulfates. None of those procedures involves the use of sulfuric acid for direct sulfation of alcohols. [0013] However, in a recent patent application (US 2011/0213081 A1), direct action of sulfuric acid has been claimed useful for partial sulfating of ethoxylated polyamines. In this process the water eliminated is removed by continuous vacuuming at 60-85 °C. Conversion yields of this interesting sulfation process can reach 25-30 % within 6-8 h, in terms of the available hydroxyl end groups. 55 [0014] US patent issued in 2002 (US 6,452,035) discloses a trans-sulfation process to produce sulfate esters from alcohols and alcoxylated amines and ethoxylated alcohols. In this process tertiary amine salts of low molecular weight dialkyl sulfates (with C1-C4) are interacted with higher alcohols and residual amines are removed by addition of equivalent sulfuric acid. 3 EP 2 851 362 B1 [0015] In a recent paper and given with reference number [1] titled "Aliphatic Thioethers by S-Alkylation of Thiols via Trialkyl Borates", it has been reported that trialkyl borates can be used for alkylation of thiols to synthesize aliphatic thioethers in the presence of sulfuric acid and pyridine. In the said paper, dialkyl sulfate has been demonstrated as an intermediate product that is consumed in the following reaction as soon as it is formed. Presence of dialkyl sulfate in the 5 mixture has been confirmed by extracting from the aliquot taken from the mixture using ether, but it is not stated that dialkyl sulfates are isolated and purified.