US2547913A - Process for the preparation of vanillin and vanillin derivatives - Google Patents

Process for the preparation of vanillin and vanillin derivatives Download PDF

Info

Publication number
US2547913A
US2547913A US144038A US14403850A US2547913A US 2547913 A US2547913 A US 2547913A US 144038 A US144038 A US 144038A US 14403850 A US14403850 A US 14403850A US 2547913 A US2547913 A US 2547913A
Authority
US
United States
Prior art keywords
parts
vanillin
volume
weight
compounds
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 - Lifetime
Application number
US144038A
Other languages
English (en)
Inventor
Lagally Paul
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.)
Aschaffenburger Zellstoffwerke AG
Original Assignee
Aschaffenburger Zellstoffwerke 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 Aschaffenburger Zellstoffwerke AG filed Critical Aschaffenburger Zellstoffwerke AG
Application granted granted Critical
Publication of US2547913A publication Critical patent/US2547913A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78Separation; Purification; Stabilisation; Use of additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00Macromolecular compounds derived from lignin, e.g. tannins, humic acids

Definitions

  • the present invention relates to a-process for the preparation of vanillin and vanillin derivatives from lignin or lignin-containing material. It is known to prepare vanillin by sublimation and alkaline boiling of lignin-containing materials. As shown more particularly by the work of Freudenberg (see, for example, Swedish Patent No. 102.171), the yields of vanillin according to this known procedure may be increased by the supplemental use of air or oxygen. A favorable yield has'also followed from the supplemental use and careful pro-port oning of other oxidizing agents.
  • a primary object of the present invention is pounds are the sulfoxides and sulfones which are the development of a process whereby the aforesaid prior art defects are obviated.
  • iodine compounds wherein the iodine atom is in an ethylene linkage.
  • Typical representatives of these iodine compounds are, for exiodosobenzene, iodobenzene, p-propyliodobenzene, p-propyl-iodosobenzene, o-iodosotoluene, o-iodotoluene, iodoso-m-xylene, iodo-mxylene, 4 iodoso-acetophenonad iodo-aceto phenone, iodoso-anisole, iodoanisole,' iodosochlorethylene, iodo-chlorethylene, iodo-fumaric acid-iodoso-chloride, iodoso-iodoacrylic acid.
  • oxygenating compounds according to the invention have an adequate solubility in water, while someof them, such as many amine oxides, are markedly hygroscopic.
  • the starting materials can be readily recovered by conventional procedures such as distillation, crystallization, etc., and can be reutilized after conversion back into the state of higher valency.
  • the preparation of the amine oxides which are preferred reactants, can be carried out with suitable oxidizing-agents such as hydrogen peroxide, Caros acid or by anodicoxidation.
  • sulfoxides and sulfones may be obtained smoothly and usually quantitatively from the sulfides by the action of hydrogen peroxide. Furthermore, many of the representatives of this class, i. e. the sulfur-containing compounds, are accessible in simple manner by Example 1
  • 1000 parts by volume of waste sulfite liquor having a dry content of 11.5%by Weight and a. density of 1.05 110 parts by weight of caustic soda-are dissolved, and 137 parts by weight of N,N- dimethylaniline-N-oxide are introduced into the so-obtained strongly alkaline liquor.
  • the obtained mixture is heated for .3 hours to 160 C. in an autoclave.
  • the reaction mixture which contains the formed vanillin in the form of sodium vanillate, is worked up as follows:
  • the re-formed dimethylaniline (115 parts by weight, equivalent to 95% of the amount used as oxide) is separated or distilled off with steam.
  • the solution is then neutralized with 100 parts by volume of commercial hydrochloric acid, excess acid neutralized with parts by weight of sodium bicarbonate, and then extracted for 8 hours with benzene under a slight vacuum. After distillation of the benzene, 6 parts by weight (equivalent to of the starting organic substance) of fairly pure vanillin crystallize out in the course of several hours.
  • acidsifying the mother liquor products are obtained which can be further Worked up into synthetic resin and tanning extract.
  • N ,N-dimethylaniline-N-oxide in this example, use may also be made in analogous manner of an equivalent amount of tripropylamine-N-oxide, N,N,N,Ntetramethyl-diaminobenzophenone-N,N'-dioxide, pyridine-N-oxide, N-methyl-piperidine-N-oxide, etc.
  • Example 2 i A mixture of 150 parts by volume of fermented and concentrated waste sulfite liquor (35 B.) obtained from pin wood, 200 parts by volume of technical caustic soda solution of 55% by volume strength (110 parts by weight of NaOI-I) and the products of the reaction between 135 parts by volume of N,N-dimethylcyclohexylamine and 85 parts'by volume of 40% by volume hydrogen peroxide, is heated to 165 C. for 3 hours in an autoclave by the forcing in of direct steam (10 .atm.).
  • reaction mixture (about 1000 parts by volume) is carried out according to- Example 1 and yields 130 parts by'volume of dimethylcyclohexylamine (96%) and, after neutralization and extraction, about 5 parts by weight of pure vanillin in addition to a series of benzenesoluble lignin decomposition products and resins.
  • Example 3 A mixture of 175 parts by volume of fermented and concentrated beechwood waste sulfite liquor with a dry content of 52% by weight, 400 parts by volume of caustic soda solution of 30% by volume strength, and the product of the reaction 4 between 63.5 parts by volume of dimethylaniline with 100 parts by volume of 35% by volume hydrogen peroxide, is heated to 165 C. for 3 hours in an autoclave. The working up of the reaction mixtur takes place as in the preceding examples.
  • Example 4 A mixture of 150 parts by volume of fermented and concentrated waste sulfite liquor obtained from pine wood, 400 parts by volume of caustic soda solution of 30% by volume strength, andthe product of the reaction between 108 parts by vol-. ume of diethyl sulfide and parts by volume of 35% by volume hydrogen peroxide, is heated to 200 C. for 10 hours in an autoclave. Upon com-.v pletion of the reaction, '76 parts by volume of diethyl sulfide are distilled off with steam and, after. neutralization and extraction with benzene, about 4 parts by Weight of fairly pure vanillin are obtained.
  • diethyl sulfoxide instead of diethyl sulfoxide, use may also be made in analogous manner of an equivalent amount of diethyl sulfone, produced from diethyl sulfide with a double quantity of hydrogen peroxide, as well as also of equivalent amounts of the sulfoxides and sulfones obtainable from di-. methyl sulfide, di-isopropyl sulfide and tetramethylen sulfide.
  • Example 5 A mixture of parts by volume of fermented. and concentrated waste sulfite liquor (35 Be.)- obtained from pine wood, 500 parts by volume of caustic soda solution of 22% strength by volume, and a suspension of 56 parts by weight of iodosobenzene in 150 parts by volume of Water, is heated to C. for 3 hours in an autoclave.
  • the Work--v ing up of the reaction mixture is effected as in the preceding examples. First, 35 parts by weight of iodobenzene are distilled off with steam; the remaining aqueous solution is neutralized with parts by volume of concentrated hydrochloric acid, and 3.2 parts by weight of crude vanillin are then extracted with benzene. After recrystallization, 2.5 parts by weight of pure vanillin are obtained.
  • the iodosobenzene used in this example may be replaced by corresponding quantities of any of the compounds of higher valent iodine hereinbefore enumerated.
  • A'process for the preparation of vanillin and vanillin derivatives from lignin which comprises heating the lignin to a temperature above'100" C. with a water-soluble organic oxygen liberating compound, liberating oxygen at a temperature of above 100 C. and selected from the group consisting of and the spent water soluble oxygen liberating compound is removed from the reaction mixture, reoxidized and recycled for use with additional lignin being treated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US144038A 1948-06-16 1950-02-13 Process for the preparation of vanillin and vanillin derivatives Expired - Lifetime US2547913A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR2547913X 1948-06-16

Publications (1)

Publication Number Publication Date
US2547913A true US2547913A (en) 1951-04-03

Family

ID=46207801

Family Applications (1)

Application Number Title Priority Date Filing Date
US144038A Expired - Lifetime US2547913A (en) 1948-06-16 1950-02-13 Process for the preparation of vanillin and vanillin derivatives

Country Status (2)

Country Link
US (1) US2547913A (fi)
FI (1) FI27541A (fi)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2750290A (en) * 1952-02-21 1956-06-12 Sterling Drug Inc Recovery of cooking liquor from spent semi-chemical pulping liquors
US2782210A (en) * 1951-07-24 1957-02-19 Teuber Hans Joachim New oxidation products of organic compounds, and a method of making same
DE1013285B (de) * 1954-04-13 1957-08-08 Schering Ag Verfahren zur Gewinnung loeslicher aromatischer Produkte aus Lignin
WO1999021810A1 (de) * 1997-10-29 1999-05-06 Olaf Gille Verfahren zur herstellung von phenolen, aldehyden, estern und/oder ketonen aus lignin und/oder ligninsulphonsäure

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2187366A (en) * 1937-02-03 1940-01-16 Schimmel & Co A G Manufacture of vanillin

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2187366A (en) * 1937-02-03 1940-01-16 Schimmel & Co A G Manufacture of vanillin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782210A (en) * 1951-07-24 1957-02-19 Teuber Hans Joachim New oxidation products of organic compounds, and a method of making same
US2750290A (en) * 1952-02-21 1956-06-12 Sterling Drug Inc Recovery of cooking liquor from spent semi-chemical pulping liquors
DE1013285B (de) * 1954-04-13 1957-08-08 Schering Ag Verfahren zur Gewinnung loeslicher aromatischer Produkte aus Lignin
WO1999021810A1 (de) * 1997-10-29 1999-05-06 Olaf Gille Verfahren zur herstellung von phenolen, aldehyden, estern und/oder ketonen aus lignin und/oder ligninsulphonsäure

Also Published As

Publication number Publication date
FI27541A (fi) 1955-03-10

Similar Documents

Publication Publication Date Title
Gresham et al. β-Propiolactone. XIII. Reactions with Sodium Nitrite, Sodium Dithionite, Sodium Cyanide, Sodium Thiocyanate, Sodium Succinimide and Aryl Sulfinic Acids and Their Salts1
US3549319A (en) Production of alkali metal sulfites or bisulfites
US2650927A (en) Process for the manufacture of epoxides
US2547913A (en) Process for the preparation of vanillin and vanillin derivatives
EP0088275B1 (de) Verfahren zur Herstellung von Trimethylolpropan
US2187366A (en) Manufacture of vanillin
Toda et al. Intramolecular Cyclization of o, o′-Dihydroxydiphenyldiacetylene
US2464600A (en) Process for preparing diphenyldihaloethanes
Pearl Reactions of Vanillin and its Derived Compounds. II. The Reaction of Vanillin with Alkali and Silver Nitrate1, 2
US2417346A (en) Degradation treatment of lignin material
US2778830A (en) Production of z-aminopyrimidines
US2285366A (en) Method of making terpene derivatives
US1792716A (en) Process of making safrol derivatives such as protocatechuic aldehyde and isoeugenol
EP0000341A1 (de) Verfahren zur Herstellung von praktisch reinem 1-Amino-8-nitro-4,5-dihydroxy-anthrachinon
US3647866A (en) Method of oxidizing a secondary alkyl-substituted toluene
US2807650A (en) 1, 1, 3-trimethylindane-3-hydroperoxide
US2769844A (en) Process for preparation of para-alphacumyl phenol
US2445500A (en) Manufacture of ethers of phenols
US2465012A (en) Manufacture of heptan-3:4-dione and ethyl propyl acrylic acid
US2028271A (en) Manufacture of para-cyclohexylphenols
DE3517158A1 (de) Methyl-2-(2-hydroperoxy-2-propyl)-naphthalin-6- carboxylat und verfahren zu dessen herstellung
US2883430A (en) Production of phenols
DE2134292C3 (de) Verfahren zum Herstellen von aliphatischen Ketonen, Aldehyden und Alkoholen
US2797249A (en) Manufacture of oxygen-containing organic compounds
US2989566A (en) Manufacture of oxygen-containing organic compounds