US3755101A - Process for the preparation of saligenol - Google Patents

Process for the preparation of saligenol Download PDF

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Publication number
US3755101A
US3755101A US00200050A US3755101DA US3755101A US 3755101 A US3755101 A US 3755101A US 00200050 A US00200050 A US 00200050A US 3755101D A US3755101D A US 3755101DA US 3755101 A US3755101 A US 3755101A
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process according
acid
cosolvent
catholyte
cathode
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M Rakoutz
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Rhone Poulenc SA
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Rhone Poulenc SA
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

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  • ABSTRACT F orelgn Application Priority Data 0v fame Saligenol is obtained by electrochemical reduction of 52 US. Cl. 204/75 Salicylic acid in a which and 511 Int. Cl c07b 29/06 C07C 29/00 me are Separated fmm each by a 58 Field of Search 204/75 Change membrane and which cahmyte iniialy 1 consists of water. a cosolvent, salicylic acid and a qua- 56] References Cited ternary ammonium salt.
  • PRQCESS FOR THE PREPARATION OF SALIGENOL a -The-pre's'ent invention-.relates to asprocess-for the preparation of'saligenol 2-.hydroxy-benzyl alcohol) by electro-chemical reduction of salicylic acid (2- hydroxy-benz oic acid).
  • the process according to the invention consists of carrying out the electrolysis in ace having an anode compartment anda cathode com'partme'nt separated frfiin'oneirhdtli'er by'a cation exchange membrane, and means-lyre, itially consisting" essentially of salicylic seawater; osolvnt and a 'quartemary ammonium saltifiiiee theelectrolysis'has 'commencedgpart 'of the salicylic ci'd'will be' converted to saligenol and the willthen',ofco'ursemontain saligenol ina'ddie othercom'ponents mentioned previously.
  • Th-n ure'of the cationfexchange membrane which separates-"the catholyte from the anolyte is not critical tiftheinventionflt'is possible to use any known cation eitliange membi-ane and, in particular, homogeneoustype membranes or heterogeneous-type membranes Which ii desi'redQCan be reinforced by a screen.
  • the e'atholyte can contain one or two liquid phases. If it contains twoliquid phases, it is preferred to carry out th proce'ss in such a way that the catholyte is in the forhFof an-emiilsion,for example by stirring or by circulating theliquid.
  • Cos ems whichxciantbe usedineludealcohols, ethers, nitriles, aliphatic amides and aliphatic; esters.
  • the cosolvent preferablycontains'oneto 10 carbon atorns.
  • Cosolvents which:can be used in a one liquid phase.;catho lyt e-,-,i;n,- elude methanol, ethanol, n-propanol, isopropanol, ace ⁇ tonitrile, l-methoxy-ethanol-Z, -.l;,;- 2- dii nethoxy-ethane, glyeol,..
  • the concentration of salicylic acid in the eatholyte is advantageously above 35 g/litre andbelow the satura; tion value in the water/cosolvent/qu'artemary ammo nium salt mixture.v in question these limiting values apply to the initial acid concentration vin discontinuous processes, and to the instantaneous acideoncentration in continuous processes. v 1
  • the quartemary ammonium salts used in the catholyte are essentially saltsof the generalfformula':
  • the radicals R fR j R R can represent linear or branched alkyl radicals, s'iich as methyl, ethyl, propyl, isopropyLbutyl, pentyl, hexyl, heptyl, octyl, 2-1ethyllhexylor dodecyl, cyeloalkyl or a'lltyl-cycloalltyl radicals such as cyclohexyl, or aryl radicals such as phenyl, tolyl or xylyL
  • Examples of cations whichmay be derived from salts of formula (I) are tetramethylammonium, trimethyle thylammoniurn, methyltriethyl-ammonium, tetraetl'iyl ammonium," tetra(n-propyl)ammoniuiri-, tetra(nbutyl')ammonium,
  • the anion A can be' -such" that AH is an inorganic acid'or anorgani'e acidJ-Examples of such inorganic undissoeiated acid 3 acids AH include sulphuric, phosphoric, pyrophosphoric, hydrochloric, hydrobromic, hydriodic, perchloric, boric and fluoboric acids.
  • organic acids AH examples include formic, malonic, methanesulphonic, ethanesulphonic, benzene-sulphonic, toluenesulphonic, methylsulphuric, ethylsulphuric acid, and salicylic acid.
  • Specific quarternary ammonium salts of formula (I) which may be used are tetramethylammonium, tetraethylammonium, tetra(n-b'utyl)ammonium, tetra(n-pentyl)ammonium, triethyl(n-hexyl)ammonium, triethyl(n-octyl)ammon'ium, triethyl(2-ethylhexyl) ammonium, and triethyl( n-dodecyl)-ammonium sulphates, phosphates and halides.
  • the catholyte can contain other products, especially products which are inert under the operating conditions and by-products of the electrochemical reduction.
  • the cathode'in the cell utilised in the process of the invention can be a metal, especially mercury or a solid amalgam of mercury.
  • an aqueous acid solution is preferably used as the anolyte.
  • the precise nature of this anolyte is not criticalclude metals and metalloids such as lead and its alloys,
  • The'cu'rrent density at the cathode is generally 1 to 25 A/dm preferably 5 to A/dm'.
  • the temperature at which the electrolysis is carried out is generally 5' to 60 C and preferably 25' to C.
  • the saligenol is isolated from the catholyte by any of the'known methods, for example by solvent extraction.
  • the cosolvent is first removed, for example by distillation,
  • the process according to the invention can be carried out continuously or discontinuously.
  • the process allows saligenol to be obtained in good electrical yields and chemical yields in a process where the electrodes, especially the cathode, are not chemically degraged by the electrolyte.
  • Saligenol is a starting material used in the synthesis of coumarine.
  • the electrical cell used is that shown in the FIGURE of the accompanying drawing.
  • the cell comprises a main trough 1 having an outer jacket 2 through which liquid at a controlled predetermined temperature may be circulated.
  • Main trough l is divided up into a cathode compartmentcontainingcatholyte 4 and cathode 3 and an anode compartment containing anolyte 7 and anode 6.
  • Catholyte 4 and anolyte-7 are separated from one another by cation exchange membrane 5 and internal cell divider 9.
  • the cathode compartment is provided with amag'netic stirrer 8, thermometer l0 and a gas outlet 12 to remove gas evolved from the cathode compartment.
  • Outlet 12 leads to a gas flow rate mea suring device (not shown).
  • the electrolysisconditions are as follows: Cathode lead amalgam discof surface area 0.6 dm' (prepared by immersing a disc of lead in a bath mercury for 10 hours) i Catholyte initially a mixture consisting of 250 cm of isopropanol 80 cm of water 45 g of salicylic acid and 30 g of tetraethylammonium bromide.
  • Cation exchange membrane heterogeneous-type membrane having a matrix of. polyvinylidene fluoride the cation exchange resin is a sulphonic resin bmd on polystyrene crosslinked with divinylbenaene' the ex change capacity of the membrane is 1.05 meg/g its substitution resistance is 9.6 0 cm! men 0.1 N aqueous solution of NaCl and 4.8 0 cm in a normal aqueous solution of NaCl the permeation selectivity of the mem- I brane, measured between two aqueous NaCl solutions which are respectively normal and half-normal, is 96.2
  • the catholyte is 20 mm of mercury, which allows the isopropanolto be removed and causes a precipitate to form.
  • the precipitate is filtered off and washed with water, and the filtrate and the wash waters are combined and neutralised (pH I 7) with sodium bicarbonate.
  • the mixture is extracted with ether, the ether phase driedby means of.
  • the yield of saligenol based on the acid converted is 66.6 percent while the electricalyield is 57.6 percent.
  • Example 1 is repeated, replacing the isopropanol by methanol and using a constant current density of 6.66 A/dm at the cathode. After passing 84,500 coulombs and treating the catholyte as described in Example 1, 11.1 g of saligenol are obtained.
  • 250 cm of water 250 cm is isopropanol 45 g of salicylic acid 40 g of tetraethylammonium bromide.
  • the current density at the cathode is constant and equal to A/dm, After passing 49,720 coulombs and treating the catholyte as described in Example 1, 7.2 g of saligenol are obtained. This corresponds to a yield based on acid converted of 79 percent and an electrical yield of 45 percent.
  • each of R R,, R and R represent identical or different hydrocarbon radicals, each having from 1 to 20 carbon atoms in their chain, or in which two of the R radicals together form a single divalent radiacal and together with the nitrogen atom to which they are attached, form a heterocyclic ring and A represents an anion.
  • the cosolvent is chemically inert under the reaction conditions towards the acid to be reduced, which is electrochemically inert at potentials of between 0 and 2.5 volts relative to the saturated calomel electrode, and which has a dielectric constant of less than 50 i 4.
  • the cosolvent is selected from the group consisting of an alcohol, an ether, a nitrile and an aliphatic acid.
  • quaternary ammonium salt is a tetra-alkylammonium sulphate, phosphate or halide in which each alkyl group contains 1-20 carbon atoms.
  • anolyte is aqueous sulphuric acid
  • the catholyte initially consists essentially tetra-alkyl-ammonium salicylic acid, water, methanol or isopropanol and a tetra-alkalyammonium bromide and electrolysis is carried out at a current density at the cathode of 5-l5 A/dm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00200050A 1970-11-19 1971-11-18 Process for the preparation of saligenol Expired - Lifetime US3755101A (en)

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FR7041498A FR2114195A5 (enrdf_load_stackoverflow) 1970-11-19 1970-11-19

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US (1) US3755101A (enrdf_load_stackoverflow)
BE (1) BE775519A (enrdf_load_stackoverflow)
CA (1) CA938247A (enrdf_load_stackoverflow)
CH (1) CH551937A (enrdf_load_stackoverflow)
DE (1) DE2157560A1 (enrdf_load_stackoverflow)
FR (1) FR2114195A5 (enrdf_load_stackoverflow)
GB (1) GB1337457A (enrdf_load_stackoverflow)
NL (1) NL7115513A (enrdf_load_stackoverflow)
SU (1) SU450396A3 (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929613A (en) * 1972-12-01 1975-12-30 Rhone Poulenc Sa Preparation of glyoxylic acid
US4684449A (en) * 1985-11-26 1987-08-04 Mitsui Toatsu Chemicals, Inc. Process for producing m-hydroxybenzyl alcohol
US5320816A (en) * 1992-10-21 1994-06-14 The Dow Chemical Company Process for absorption of sulfur dioxide and nitric oxide from flue gas

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0311162D0 (en) * 2003-05-15 2003-06-18 Tyman John H P The solvent extraction of boric acid by complexation with 1,3- and with 1,2- diols derived by semi-synthesis and by separation from natural phenolic lipids
RU2567244C1 (ru) * 2014-12-30 2015-11-10 Федеральное государственное бюджетное учреждение "33 Центральный научно-исследовательский испытательный институт Министерства обороны Российской Федерации" Способ получения o-гидроксибензилового спирта (салигенина)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12654A (en) * 1855-04-03 Improved arrangement of means for freeing steam-boilers from sediments
US815193A (en) * 1905-10-11 1906-03-13 Basf Ag Production of aromatic alcohols.
US3193480A (en) * 1963-02-01 1965-07-06 Monsanto Co Adiponitrile process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12654A (en) * 1855-04-03 Improved arrangement of means for freeing steam-boilers from sediments
US815193A (en) * 1905-10-11 1906-03-13 Basf Ag Production of aromatic alcohols.
US3193480A (en) * 1963-02-01 1965-07-06 Monsanto Co Adiponitrile process

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929613A (en) * 1972-12-01 1975-12-30 Rhone Poulenc Sa Preparation of glyoxylic acid
US4684449A (en) * 1985-11-26 1987-08-04 Mitsui Toatsu Chemicals, Inc. Process for producing m-hydroxybenzyl alcohol
US5320816A (en) * 1992-10-21 1994-06-14 The Dow Chemical Company Process for absorption of sulfur dioxide and nitric oxide from flue gas

Also Published As

Publication number Publication date
DE2157560A1 (de) 1972-05-31
CH551937A (fr) 1974-07-31
GB1337457A (en) 1973-11-14
FR2114195A5 (enrdf_load_stackoverflow) 1972-06-30
CA938247A (en) 1973-12-11
BE775519A (fr) 1972-03-18
NL7115513A (enrdf_load_stackoverflow) 1972-05-24
SU450396A3 (ru) 1974-11-15

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