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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Expired - Lifetime
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US00200050A
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English (en)
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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
    • 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
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds

Definitions

  • 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 (enExample) 1970-11-19 1970-11-19

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

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

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

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