GB1586677A - Manufacture of n-(3,4-dimethylphenyl)-d-ribamine - Google Patents
Manufacture of n-(3,4-dimethylphenyl)-d-ribamine Download PDFInfo
- Publication number
- GB1586677A GB1586677A GB45920/77A GB4592077A GB1586677A GB 1586677 A GB1586677 A GB 1586677A GB 45920/77 A GB45920/77 A GB 45920/77A GB 4592077 A GB4592077 A GB 4592077A GB 1586677 A GB1586677 A GB 1586677A
- Authority
- GB
- United Kingdom
- Prior art keywords
- ribamine
- dimethylphenyl
- lactone
- dimethylnitrobenzene
- partially reduced
- 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
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- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- QXKAIJAYHKCRRA-BXXZVTAOSA-N D-ribonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)C(O)=O QXKAIJAYHKCRRA-BXXZVTAOSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- HFZKOYWDLDYELC-UHFFFAOYSA-N 1,2-dimethyl-4-nitrobenzene Chemical class CC1=CC=C([N+]([O-])=O)C=C1C HFZKOYWDLDYELC-UHFFFAOYSA-N 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- -1 hydrazo Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- WEVSWJHEFVKUSR-UHFFFAOYSA-N bis(3,4-dimethylphenyl)diazene Chemical compound C1=C(C)C(C)=CC=C1N=NC1=CC=C(C)C(C)=C1 WEVSWJHEFVKUSR-UHFFFAOYSA-N 0.000 claims description 7
- NVDICYFEQBBCOH-UHFFFAOYSA-N (3,4-dimethylphenyl)-(3,4-dimethylphenyl)imino-oxidoazanium Chemical compound C1=C(C)C(C)=CC=C1N=[N+]([O-])C1=CC=C(C)C(C)=C1 NVDICYFEQBBCOH-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 4
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims description 3
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical group N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002329 infrared spectrum Methods 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 5
- CUOKHACJLGPRHD-BXXZVTAOSA-N D-ribono-1,4-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H]1O CUOKHACJLGPRHD-BXXZVTAOSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical compound CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- PYMYPHUHKUWMLA-LMVFSUKVSA-N aldehydo-D-ribose Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- QNRFMBRRBOYLJH-IJLUTSLNSA-N (2r,3r,4r)-n-(3,4-dimethylphenyl)-2,3,4,5-tetrahydroxypentanamide Chemical compound CC1=CC=C(NC(=O)[C@H](O)[C@H](O)[C@H](O)CO)C=C1C QNRFMBRRBOYLJH-IJLUTSLNSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- FWXNGZXYKWNRQM-UHFFFAOYSA-N 1,2-bis(3,4-dimethylphenyl)hydrazine Chemical compound C1=C(C)C(C)=CC=C1NNC1=CC=C(C)C(C)=C1 FWXNGZXYKWNRQM-UHFFFAOYSA-N 0.000 description 1
- BIJJCIFZOOLNRN-UHFFFAOYSA-N 1,2-dimethyl-4-nitrosobenzene Chemical compound CC1=CC=C(N=O)C=C1C BIJJCIFZOOLNRN-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- WIGIZIANZCJQQY-UHFFFAOYSA-N 4-ethyl-3-methyl-N-[2-[4-[[[(4-methylcyclohexyl)amino]-oxomethyl]sulfamoyl]phenyl]ethyl]-5-oxo-2H-pyrrole-1-carboxamide Chemical compound O=C1C(CC)=C(C)CN1C(=O)NCCC1=CC=C(S(=O)(=O)NC(=O)NC2CCC(C)CC2)C=C1 WIGIZIANZCJQQY-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QXKAIJAYHKCRRA-JJYYJPOSSA-N D-arabinonic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(O)=O QXKAIJAYHKCRRA-JJYYJPOSSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000006345 epimerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- OMQHMQCZNLHYAG-UHFFFAOYSA-N n-(3,4-dimethylphenyl)hydroxylamine Chemical group CC1=CC=C(NO)C=C1C OMQHMQCZNLHYAG-UHFFFAOYSA-N 0.000 description 1
- CVUXFFLDBKALLQ-UHFFFAOYSA-N n-[(3,4-dimethylphenyl)diazenyl]-3,4-dimethylaniline Chemical compound C1=C(C)C(C)=CC=C1NN=NC1=CC=C(C)C(C)=C1 CVUXFFLDBKALLQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
N-[3,4-dimethylphenyl]-D-ribamine of the formula I is prepared in pure form and with a good yield by the catalytic hydrogenation of D-ribono- gamma -lactone. The reaction is carried out in the presence of an organic solvent and a 3,4-dimethylbenzene derivative whose nitro group is partially reduced. The symbols of the formula I have the meaning given in Patent Claim 1. <IMAGE>
Description
(54) MANUFACTURE OF N-[3,4-DIMETHYLPHENYL]-D-RIBAMINE (71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock Company of 6700
Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
The present invention relates to a new process for the manufacture of N-[3,4dimethylphenyl]-D-ribamine of the formula I
N-[3,4-Dimethylphenyll-D-ribamine, an important intermediate for the manufacture of vitamin B 2 can be manufactured, for example, in accordance with a process disclosed in
U.S. Patent 2,384,105, by reacting D-ribose and 3,4-dimethylaniline, followed by catalytic hydrogenation at up to 100"C. Since, as is known, D-ribose is difficult to obtain, U.S.
Patent 2,411,611 discloses a process wherein 3,4-dimethylaniline is condensed with
D-ribonic acid y-lactone to give D-ribonic acid 3,4-dimethylanilide. N-[3,4
Dimethylphenyl]-D-ribamine is then manufactured from the anilide by acetylation, chlorination, hydrogenation and deacetylation. N-[3,4-Dimethylphenyl]-D-ribamine cannot be manufactured economically by this involved process.
It has also already been proposed to hydrogenate a mixture of 3,4-dimethylaniline, or the corresponding nitro compound. with D-ribonic acid y-lactone in an inert solvent, using platinum oxide. This process, which is disclosed in U.S. Patent 2,422,997 and which is carried out at below 1()() C to avoid side-reactions, gives moderate yields of N-[3,4 dimethylphenyl]-D-ribamine.
The earlier German Laid-Open Application DOS 2,558,515, which does not constitute a prior disclosure, describes a process in which N-[3,4-dimethylphenyl]-D-ribamine is obtained by catalytic hydrogenation of a mixture of 3,4-dimethylaniline and/or 3,4-dimethyl-nitrobenzene and D-ribonic acid, its esters or D-ribonic acid y-lactone at from 100 to 155"C. If 3,4-dimethylnitrobenzene is used as the starting material for this process, the yields are unsatisfactory. If 3.4-dimethylaniline is used, side-reactions cannot be excluded. Thus. 3,4-dimethylaniline may react with D-ribonic acid y-lactone to give
D-ribonic acid 3,4-dimethylanilide (J.Chem.Soc.1945,167). Furthermore, at about 1300C 3,4-dimethylaniline catalyzes the epimerization of D-ribonic acid y-lactone to D-arabonic acid y-lactone, which in the presence of 3,4-dimethylaniline undergoes hydrogenation to give the undesired product N-[3.4-dimethylphenyl]-D-arabinamine.
We have found that N-(3q4-dimethylphenyl)-D-ribamine of the formula I
can be manufactured particularly advantageously by a method wherein D-ribonic acid y-lactone is catalytically hydrogenated in an organic solvent and in the presence of a 3,4-dimethylnitrobenzene derivative in which the nitro group is partially reduced.
Examples of 3,4-dimethylnitrobenzene derivatives in which the nitro group is partially reduced are derivatives of 3,4-dimethyl-benzene which contain an azoxy, azo, hydrazo, nitroso, hydroxylamino or diazoamino group in the 1-position, i.e. the compounds of the general formula II
where X is one of the radicals -NO, -NHOH, -NH-N=N-R, -NH-NH-R, -N=N-R and -NO=N-R, and R is 3,4-dimethylphenyl.
The following compounds are examples,of starting materials of the general formula II: 3,4,3' ,4'-tetramethylazoxybenzene, 3,4,3' ,4'-tetramethylazobenzene, 3,4,3' 4'- tetramethylhydrazobenzene, 3,4-dimethylnitrosobenzene, 3,4,3',4'- tetramethyldiazoaminobenzene and 4-hydroxylamino-o-xylene. Of these compounds, 3,4,3',4'-tetramethylazoxybenzene and 3,4,3' ,4'-tetramethylazobenzene are preferred.
Suitable solvents are conventional organic solvents which undergo little or no change under the catalytic hydrogenation conditions. Examples are alcohols, eg. methanol, ethanol, propanol and butanol, or ethers, eg. dioxane, the latter being the preferred solvent.
Examples of catalysts which may be used for the catalytic hydrogenation are metals from amongst the transition elements, eg. copper, chromium, nickel, iron, platinum, palladium, rhodium, cerium, thorium and zinc, the metals aluminum and magnesium and the oxides of the said metals. Mixtures of the said metals or.metal oxides, for example the mixed oxides described in Schwab: "Handbuch der Katalyse", Volume 5, pages 567-577, are also very suitable. Copper oxide and/or copper-containing catalysts, especially those which contain finely divided copper oxide and/or copper on a catalyst carrier, have proved particularly advantageous. Examples of carriers present in these catalysts are refractory oxides, e.g.
chromium oxide, aluminum oxide or cerium oxide. Such catalysts are described, for example, by H. Adkins in Organic Reactions, Volume VIII, 1954, pages 8 and 9 and in
German Laid-Open Application DOS 2,024,282. Amongst these catalysts, those containing copper oxide and chromium oxide and those containing copper oxide and aluminum oxide are very suitable.
It is particularly advantageous to treat the catalysts with hydrogen before they are used.
This prehydrogenation is carried out at. for example, up to 400"C, preferably at from 150 to 2500C and under a hydrogen pressure of from 0.01 bar (in the absence of a solvent) to 300 bars (in the case of a suspension in a solvent).
The hydrogenation according to the invention is preferably carried out at from 70 to 160"C, above all at from 125 to 145 C. The hydrogen pressure is advantageously from 1 to 1,000, preferably from 100 to 300 bars. Advantageously, the starting materials are reacted in the stoichiometric ratio. Advantageously, from 100 to 400 parts by weight of solvent are used per 100 parts by weight of the mixture of the starting materials.
The process of the invention is able to give pure N-[3,4-dimethylphenyll-D-ribamine in good yield. N-[3.4-dimethylphenyll-D-ribamine thus obtained may be converted into vitamin B 2 by the methods described in J. Fragner: Vitamine, Volume II, G. Fischer
Verlag, Jena, page 1381.
Example 1
Hydrogenation of 3,4,3',4'-tetramethyl-azoxy-benzene with D-ribonic acid y-lactone to give N-[3,4-dimethylphenyl]-D-ribamine
18 g of a copper oxide/aluminum oxide catalyst are pre-hydrogenated in 150 ml of dioxane for 8 hours at 2000C under 150 bars hydrogen pressure. 12.7 g (0.05 mole) of 3,4,3',4'-tetramethyl-azoxy-benzene and 14.8 g (0.1 mole) of D-ribonic acid y-lactone are then added and the mixture is hydrogenated for 24 hours at 135"C and 250 bars hydrogen pressure. After completion of the hydrogenation, and after cooling, 125 ml of ethanol are added and the mixture is heated in order to dissolve the partially precipitated N-[3,4-dimethylphenylj-D-ribamine. The catalyst is filtered off, the filtrate is concentrated and the residue is recrystallized from ethanol.
Yield: 70% of N-[3,4-dimethylphenyl]-D-ribamine [a]D = -23.54" (C = 0.4; methanol)
Analysis C13H21NO4, molecular weight: 255.31 %C %H %O %N
calculated: 61.1 .8.1 25.1 5.9
found: 61.15 8.29 25.07 5.49 l3C-NMR spectrum (DDMSO; TMS-standard): chemical shift (ppm): 147.2; 136.0; 129.8; 122.8; 114.1; 109.9; 73.5; 72.8; 70.3; 63.2; 46.0; 19.7; 18.3.
Example 2
Hydrogenation of 3,4,3' ,4'-tetramethylhydrazobenzene with D-ribonic acid y-lactone to give N-[3 ,4-dimethylphenyl]-D-ribamine
24.03 g (0.1 mole) of 3,4,3'*4'-tetramethylhydrazobenzene and 29.6 g (0.2 mole) of
D-ribonic acid y-lactone are hydrogenated with 18 g of a copper oxide/aluminum oxide catalyst, which has been prehydrogenated as described in Example 1, for 24 hours at 1350C and 290 bars hydrogen pressure. The mixture is worked up as described in Example 1.
Yield: 75% of N-[3,4-dimthylphenyl]-D-ribamine Example 3
Hydrogenation of 3,4,3' ,4'-tetramethylazobenzene with D-ribonic acid y-lactone to give N-[3.4-dimethylphenyl]-D-ribamine
29.6 g (0.2 mole) of D-ribonic acid y-lactone and 23.8 g (0.1 mole) of 3,4,3',4'tetramethylazobenzene are hydrogenated with 18 g of a copper oxide catalyst (which has been prehydrogenated for 8 hours at 200"C in dioxane), for 24 hours at 135"C under 300 bars hydrogen pressure. After completion of the hydrogenation, 300 ml of ethanol are added, the mixture is heated, the catalyst is filtered off and the filtrate is concentrated, The residue is recrystallized from 150 ml of ethanol.
Yield: 60% of N-[3,4-dimethylphenyl]-D-ribamine.
The IR spectrum and '3C-NMR spectrum agree with the structure of N-[3,4 dim ethylphenyl]-D-ribamine.
Analysis: Cl3H2,NO4 %C %H %O %N
calculated: 61.1 8.1 25.3 5.3
found: 61.15 8.29 25.07 5 49
WHAT WE CLAIM IS:
1. A process for the manufacture of N-[3,4-dimethylphenyl]-D-ribamine of the formula
in which D-ribonic acid y-lactone is catalytically hydrogenated in an organic solvent and in the presence of a 3,4-dimethylnitrobenzene derivative in which the nitro group is partially reduced.
2. A process as claimed in claim 1, in which the partially reduced derivative of 3,4-dimethylnitrobenzene is a 3,4-dimethylbenzene which has an azoxy, azo, hydrazo, nitroso, hydroxylamino or diazoamine group in the 1-position.
3. A process as claimed in claim 1, in which 3,4,3',4'-tetramethylazoxybenzene or 3,4,3',4'-tetramethylazobenzene is used as the partially reduced 3,4-dimethylnitrobenzene derivative.
4. A process as claimed in any of claims 1 to 3, in which the hydrogenation is carried out with a catalyst which contains copper oxide and/or copper.
5. A process for the manufacture of N-[3,4-dimethylphenyl]-D-ribamine carried out substantially as described in any of the foregoing Examples.
6. N-[3,4-dimethylphenyl]-D-ribamine when manufactured by a process as claimed in any of claims 1 to 5.
7 Vitamin B 2 when obtained from N-[3 ,4-dimethylphenyl]-D-ribamine manufactured by a process as claimed in any of claims 1 to 5.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (6)
1. A process for the manufacture of N-[3,4-dimethylphenyl]-D-ribamine of the formula
in which D-ribonic acid y-lactone is catalytically hydrogenated in an organic solvent and in the presence of a 3,4-dimethylnitrobenzene derivative in which the nitro group is partially reduced.
2. A process as claimed in claim 1, in which the partially reduced derivative of 3,4-dimethylnitrobenzene is a 3,4-dimethylbenzene which has an azoxy, azo, hydrazo, nitroso, hydroxylamino or diazoamine group in the 1-position.
3. A process as claimed in claim 1, in which 3,4,3',4'-tetramethylazoxybenzene or 3,4,3',4'-tetramethylazobenzene is used as the partially reduced 3,4-dimethylnitrobenzene derivative.
4. A process as claimed in any of claims 1 to 3, in which the hydrogenation is carried out with a catalyst which contains copper oxide and/or copper.
5. A process for the manufacture of N-[3,4-dimethylphenyl]-D-ribamine carried out substantially as described in any of the foregoing Examples.
6. N-[3,4-dimethylphenyl]-D-ribamine when manufactured by a process as claimed in any of claims 1 to 5.
7 Vitamin B 2 when obtained from N-[3 ,4-dimethylphenyl]-D-ribamine manufactured by a process as claimed in any of claims 1 to 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762650830 DE2650830A1 (en) | 1976-11-06 | 1976-11-06 | METHOD OF MANUFACTURING ANGULAR CLAMP ON 3,4-DIMETHYLPHENYL ANGLE CLAMP TO -D-RIBAMINE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1586677A true GB1586677A (en) | 1981-03-25 |
Family
ID=5992572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB45920/77A Expired GB1586677A (en) | 1976-11-06 | 1977-11-04 | Manufacture of n-(3,4-dimethylphenyl)-d-ribamine |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5359632A (en) |
| CA (1) | CA1101887A (en) |
| CH (1) | CH630602A5 (en) |
| DE (1) | DE2650830A1 (en) |
| FR (1) | FR2370033A1 (en) |
| GB (1) | GB1586677A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL60827C (en) * | 1944-12-15 | |||
| NL7614211A (en) * | 1975-12-24 | 1977-06-28 | Basf Ag | PROCESS FOR THE PREPARATION OF N- (3,4-DIMETHYL-PHENYL) -D-RIBAMINE. |
| DE2558515C3 (en) * | 1975-12-24 | 1979-02-01 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of N- [3,4-dimethylphenyl] D-ribamine |
-
1976
- 1976-11-06 DE DE19762650830 patent/DE2650830A1/en not_active Withdrawn
-
1977
- 1977-10-11 CA CA288,684A patent/CA1101887A/en not_active Expired
- 1977-10-31 JP JP12978977A patent/JPS5359632A/en active Pending
- 1977-11-02 CH CH1336377A patent/CH630602A5/en not_active IP Right Cessation
- 1977-11-03 FR FR7732982A patent/FR2370033A1/en active Granted
- 1977-11-04 GB GB45920/77A patent/GB1586677A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CH630602A5 (en) | 1982-06-30 |
| JPS5359632A (en) | 1978-05-29 |
| FR2370033A1 (en) | 1978-06-02 |
| DE2650830A1 (en) | 1978-05-11 |
| CA1101887A (en) | 1981-05-26 |
| FR2370033B1 (en) | 1981-12-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |