US2547913A - Process for the preparation of vanillin and vanillin derivatives - Google Patents
Process for the preparation of vanillin and vanillin derivatives Download PDFInfo
- 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
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- United States
- Prior art keywords
- parts
- vanillin
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- weight
- compounds
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- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular 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.
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- 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)
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)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2187366A (en) * | 1937-02-03 | 1940-01-16 | Schimmel & Co A G | Manufacture of vanillin |
-
1949
- 1949-10-24 FI FI157349A patent/FI27541A/fi unknown
-
1950
- 1950-02-13 US US144038A patent/US2547913A/en not_active Expired - Lifetime
Patent Citations (1)
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)
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 |
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