CA2188655A1 - Oxidative ammonolysis of alkylpyridines - Google Patents
Oxidative ammonolysis of alkylpyridinesInfo
- Publication number
- CA2188655A1 CA2188655A1 CA002188655A CA2188655A CA2188655A1 CA 2188655 A1 CA2188655 A1 CA 2188655A1 CA 002188655 A CA002188655 A CA 002188655A CA 2188655 A CA2188655 A CA 2188655A CA 2188655 A1 CA2188655 A1 CA 2188655A1
- Authority
- CA
- Canada
- Prior art keywords
- catalytic composition
- process according
- methyl
- ammonia
- catalyst
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
Abstract
A process for the preparation of a highly selective catalyst and its application in the production of cyanopyridines by oxidative ammonolysis of alkylpyridines is described. The catalytic composition is defined by the formula: Va Tib Zrc Ox, wherein a is 1, b is 7.5 to 8, c is 0 to 0.5, x represents the number of oxygen atoms necessary to satisfy the valency requirements of the elements present.
Description
woss/320s4 Zt 886~ PcrlEP94/02677 Oxidativç~ ofal~vl~Y~
This invention relates to a process for the preparation of a highly selGctive catalyst for the production of ~Y~I~IUIJ~'iU;~ by oxidative ~y ,;~ of dlh,~p,y~id;~ and to 8 process for the preparation of ~ lUIJy ' '' The invention is especially directed to the production of 3-~_y~lu~JJ .il;--~ or , ", . id;--t derivatives which are important precursors for nicotinic acid or nicotirlic acid amide. Nicotinic acid or nicotirlic acid amide gre essential vitamins of the B-complex, Oxidative ~IIIllll~lUI,~ ..;.~ of alk~ yl hl;.._., is well known in the art. A great variety of catalyst systems and processes there to have been disclosed but so far no process is known which can satisfy the needs of a commercial process on technical scale.
Reference is made to British patent GB I 317 064 wherein a mixed oxide catalyst of vanadium oxide and titanium oxide having a molar ratio of 1:0.6 to 1:32 is disclosed for the oxidative ~.4..~..r,1,r~;~ of ~ 'pyl ' ' The maxiumum yield of ~,J . " .hl;-~-, achieved for the conversion of 3~ !,u,.id;..~i was 89%(example42;V205:TiO2=1:l6)andfortheconversionof2-methyl-s-~ !iJ
61% (example 54; V25:Ti2 = 1 :4) The results are obtained with this known process cannot satisfy especially with rçspect to selectivity, yield. and feed rates of alkyl~, ' ' The object of the present invention therefore is to provide a highiy selective ' ' catalyst and an improved process for the conversion of '~,lpy.;d;~ by oxidative ammono-lysis.
The drawbacks could be overcome by a highly active catalyst prepared according to claim I
and with an oxidative d~ u~ul,y~ process according to claim 7, The preparation of the catalytic composition defined by the formula Va Tib Zrc x wherein a is I
J b is 7.5to8 c is 0 to 0.5 x represents the number of oxygen atoms necessary to satisfy the valency l ~ .L~ of the elements preSent SUBSTITUTE SHEET (RULE 26) wo 9~/320s4 2 1 8 8 6 5~ PCT/EP94/02677 follows according to claim I the steps of ~ . e~;~J;Ld~ a solution of a V5+- and of a Ti4+-and optionally of a Zr4+-compound in water with a solution of ammonia in water, by a subsequent exposure ofthe precipitate to a drying treatment and to a hcat trcatment and by a shaping step in order to bring the catalytic composition in a suitable cataiyst forrn.
Suitabie sourees of the titanium component are preferably water soluble Ti4+-eompounds such æ ~ ;L~u~u~l~vl v-,u~ie, i or organic Ti-compounds sueh æ Ti-le~ v~
uitable sources of the vanadium eomponent are water soluble V5+-compounds, for example 4u14Jdtti.
A suitable souree for the zireonium component is preferably a water soluble Zr4+-compound such as ~ u..u",v~I,iu,idc.
The cu~. e-,;L~i~41ioll taices place by a ~,., ...11~, ...,. ~ mixing of the dissoived eataiyst eomponents with an ammonia water solution in sueh a manner that after the ,vl., c~ 41ivll the pl~ of the liquid is between 8 and 9.
The preeipitate formed ean then be separated by i~nown means and afterwards either first dried, preferablyinanairstreamatt~.--y.,.4~UIc.between 120Cand 140C,ordireetlyexposedtoa heat treatment at ~ ul c . between 360C to 400C, preferably in presenee of air. Then a common shaping step can foliow in order to suitably mould the catalyst.
Preferably tablets are formed whieh are dJ~4 I~4~VU .l~ exposcd to a further heat trcatment at ~.,.IIlJ.,.~lLul~:~ between 740C and 850C in the presence of air.
The ready prepared eatalytic ~ ean then be loaded into the reactor, wherein after an activation phase under reaetion conditions, it is able to ri,~mrm~tr~tl~ its properties with respeet to high activity and selectivity at high loads of the ali~ ,J . iJ;I~e, and with respect to long life-time.
Preferred catalytic ~ v -l -,~li.,,. are:
V Ti8 X
V Ti7 5 Zro 5 x V Ti7 5 Zro l25 x whrein x is as deflned before.
SUBSTITUTE SHEET ~RULE 26 WO 95132054 2 1 ~ ~ 6 ~ r~ 07~;77 The most preferred catalytic l,~lllL.Iu~;liOll is:
V Ti8 x wherein x is as defined before.
The process of the present invention is appiicable fo} the conversion of a wide variety of I " YI~J~;U..._~ to ~,y~luL~ in~s Suitable: " yl~.iJ;l~ are e.g. 3 ' J~.; i;,.~, 3-ethyl-pyridine, 2-methyl-5~ .J.;d;..c, 2,5-d;~ ll-yl~y~; i;--c and 2-methyl-5-v;.-Jl~,J ' Most preferred -" YI~J ` ' are the 3-...~.J!1,~,;J;.~ and the 2-methyl-5~ J'~J.; i;..c.
The following process conditions have been proved to be suitable.
The gaseous feed is composed of the respective ~ J. ;Jul~, of an oxygen containing gas, ammonia and water vapour.
In general air will be used as oxygen containing gas. Thus air offers the advantage that oxygen is already diluted with inert ~-nmr~ n~c Incaseoftheconversionof3-lll~ll,ylpJ ' to3-~y~,---,~J.-J;--cthegaseousfeedis expediently composed of 3 ' J ~ ; i;llc, air (calculated to 2). ammonia, water vapour in a molar ratio from 1:7:3:3 to 1:40:10:45.
Preferablyratiorangesfrom 1:10:4:10to 1:30:7:30.
In case of the conversion of 2-methyl-5-c~ to 3-.,~ , ~y ' and depending on the reaction conditions also to 2,5-d;.~--lV~ ;llc the gaceous feed is expediently composed of
This invention relates to a process for the preparation of a highly selGctive catalyst for the production of ~Y~I~IUIJ~'iU;~ by oxidative ~y ,;~ of dlh,~p,y~id;~ and to 8 process for the preparation of ~ lUIJy ' '' The invention is especially directed to the production of 3-~_y~lu~JJ .il;--~ or , ", . id;--t derivatives which are important precursors for nicotinic acid or nicotirlic acid amide. Nicotinic acid or nicotirlic acid amide gre essential vitamins of the B-complex, Oxidative ~IIIllll~lUI,~ ..;.~ of alk~ yl hl;.._., is well known in the art. A great variety of catalyst systems and processes there to have been disclosed but so far no process is known which can satisfy the needs of a commercial process on technical scale.
Reference is made to British patent GB I 317 064 wherein a mixed oxide catalyst of vanadium oxide and titanium oxide having a molar ratio of 1:0.6 to 1:32 is disclosed for the oxidative ~.4..~..r,1,r~;~ of ~ 'pyl ' ' The maxiumum yield of ~,J . " .hl;-~-, achieved for the conversion of 3~ !,u,.id;..~i was 89%(example42;V205:TiO2=1:l6)andfortheconversionof2-methyl-s-~ !iJ
61% (example 54; V25:Ti2 = 1 :4) The results are obtained with this known process cannot satisfy especially with rçspect to selectivity, yield. and feed rates of alkyl~, ' ' The object of the present invention therefore is to provide a highiy selective ' ' catalyst and an improved process for the conversion of '~,lpy.;d;~ by oxidative ammono-lysis.
The drawbacks could be overcome by a highly active catalyst prepared according to claim I
and with an oxidative d~ u~ul,y~ process according to claim 7, The preparation of the catalytic composition defined by the formula Va Tib Zrc x wherein a is I
J b is 7.5to8 c is 0 to 0.5 x represents the number of oxygen atoms necessary to satisfy the valency l ~ .L~ of the elements preSent SUBSTITUTE SHEET (RULE 26) wo 9~/320s4 2 1 8 8 6 5~ PCT/EP94/02677 follows according to claim I the steps of ~ . e~;~J;Ld~ a solution of a V5+- and of a Ti4+-and optionally of a Zr4+-compound in water with a solution of ammonia in water, by a subsequent exposure ofthe precipitate to a drying treatment and to a hcat trcatment and by a shaping step in order to bring the catalytic composition in a suitable cataiyst forrn.
Suitabie sourees of the titanium component are preferably water soluble Ti4+-eompounds such æ ~ ;L~u~u~l~vl v-,u~ie, i or organic Ti-compounds sueh æ Ti-le~ v~
uitable sources of the vanadium eomponent are water soluble V5+-compounds, for example 4u14Jdtti.
A suitable souree for the zireonium component is preferably a water soluble Zr4+-compound such as ~ u..u",v~I,iu,idc.
The cu~. e-,;L~i~41ioll taices place by a ~,., ...11~, ...,. ~ mixing of the dissoived eataiyst eomponents with an ammonia water solution in sueh a manner that after the ,vl., c~ 41ivll the pl~ of the liquid is between 8 and 9.
The preeipitate formed ean then be separated by i~nown means and afterwards either first dried, preferablyinanairstreamatt~.--y.,.4~UIc.between 120Cand 140C,ordireetlyexposedtoa heat treatment at ~ ul c . between 360C to 400C, preferably in presenee of air. Then a common shaping step can foliow in order to suitably mould the catalyst.
Preferably tablets are formed whieh are dJ~4 I~4~VU .l~ exposcd to a further heat trcatment at ~.,.IIlJ.,.~lLul~:~ between 740C and 850C in the presence of air.
The ready prepared eatalytic ~ ean then be loaded into the reactor, wherein after an activation phase under reaetion conditions, it is able to ri,~mrm~tr~tl~ its properties with respeet to high activity and selectivity at high loads of the ali~ ,J . iJ;I~e, and with respect to long life-time.
Preferred catalytic ~ v -l -,~li.,,. are:
V Ti8 X
V Ti7 5 Zro 5 x V Ti7 5 Zro l25 x whrein x is as deflned before.
SUBSTITUTE SHEET ~RULE 26 WO 95132054 2 1 ~ ~ 6 ~ r~ 07~;77 The most preferred catalytic l,~lllL.Iu~;liOll is:
V Ti8 x wherein x is as defined before.
The process of the present invention is appiicable fo} the conversion of a wide variety of I " YI~J~;U..._~ to ~,y~luL~ in~s Suitable: " yl~.iJ;l~ are e.g. 3 ' J~.; i;,.~, 3-ethyl-pyridine, 2-methyl-5~ .J.;d;..c, 2,5-d;~ ll-yl~y~; i;--c and 2-methyl-5-v;.-Jl~,J ' Most preferred -" YI~J ` ' are the 3-...~.J!1,~,;J;.~ and the 2-methyl-5~ J'~J.; i;..c.
The following process conditions have been proved to be suitable.
The gaseous feed is composed of the respective ~ J. ;Jul~, of an oxygen containing gas, ammonia and water vapour.
In general air will be used as oxygen containing gas. Thus air offers the advantage that oxygen is already diluted with inert ~-nmr~ n~c Incaseoftheconversionof3-lll~ll,ylpJ ' to3-~y~,---,~J.-J;--cthegaseousfeedis expediently composed of 3 ' J ~ ; i;llc, air (calculated to 2). ammonia, water vapour in a molar ratio from 1:7:3:3 to 1:40:10:45.
Preferablyratiorangesfrom 1:10:4:10to 1:30:7:30.
In case of the conversion of 2-methyl-5-c~ to 3-.,~ , ~y ' and depending on the reaction conditions also to 2,5-d;.~--lV~ ;llc the gaceous feed is expediently composed of
2-methyl-5-t:ll,.yl~,y,;,i;,,c, air (calculated to 2). ammonia, water vapour in a molar ratio from 1:15:5:20 to 1:70:40:140.
The le~ ul c in the reaction zone of the catalyst ranges as a rule between 330C and 440C, preferably between 350C and 410C.
Due to the stable catalyst ~ with respect to life-time, the process according to the present invention can run continously over a long time on a large-scale basis.
he maximum molar yields achievable reach about 95% to 97% for the conversion of 3-c and about 75% for the conversion of 2-methyl-5-cl~J'pJ .; i;"c SUBSTITUTE SHEET (RULE 26~
Wo 9S/32054 2 1 8 8 6 5 5 ~ r ~ ~ fi77 The resulting :yall ~L)yl idill~, i. e. the 3-~yal~ yl idillc and/or the 2,5~ ydl~u~yl idille~ can be directly converted to nicotinic acid by a common hydrolysis trealment ~ith a base.
A nicotinic acid yield of up to 95%. based on 3-methylpyridines, can accordingly be reached.
SUE;STITUTE SHEET (RULE 26) woss/320s4 2 1 8~6 S5 r~ 7, Examples: -catalYst prer,ar~ n a) V Ti8 x catalyst:
690.4 g (3.64 mol) l;l, ,,,.. l,l. ";.l~ is slowly mixed with 400 mi water at a temperature of about 60C to 65C. Water is added to a totai volume of 800 mi.
i n a separate vessel 53 .19 g (0.45 mol) ~,J~Le iS dissolved in 850 mi water and 300 mi of a solution of ammonia in water under ref ux conditions.
During this procedure ammonia is introduced into the solution.
The solution containing the V-compound is added to the Ti-soiution at about 80C to 85C.
Water is added to a total volume of 4 litres.
In a cylinder reactor ~ith mrxing elements 670 mi of the Ti-V-solution having a temperature of 80C to 85C is mixed with 670 mi of a 5.2 % solution of ammonia in water. The wl,- cL;~;l.,le formed is filtered off, washed with water and then dried in an air stream at a temperature of 120C to 140C.
The resulting powder is then treated in a furnace at a temperature of 360C in presence of air over 2 hours, subsequently milled in a ball mill and finaily moistened with water and moulded to tabiets ~ith dimensions 4 x 4 mm. The tablets are treated in a muffe furnace in presence of air at a temperature of 740C for 2 hours.
Fresh prepared catalyst is then activated under oxidative l l~/a;~ conditions with 3-.;Li;.le.
b) V Ti7 5 Zro 5 x cataiyst:
The V-Ti-soiution is prepared as mentioned under a) In a separate vessel 73.27g (0.23 mol) ~IIculllulllo~y~ ' ' ' ' 8 H20 is dissolved in 600 mi of water at tt~ iUl L~ between 40C and 45C.
The w~ L;ull is performed in a Lul ~e~uull i;llg manner as mentioned under a) by mrxing 625 mi of the Ti-V-solution, 100 mi of the Zr-solution and 725 mi of the respective solution of ammonia in water. The further work up of the resulting precipitate is performed as mentioned under a).
V Ti7 5 Zrû 125 Oy catalyst:
SUBSTITUTE SHEET (RULE 26) WO 9~132054 2 1 8 ~ 6 5 S r~ IA7~77 The procedure of example b) was repeated except that for the wp~ d~iU~I 625 ml of the Ti-V-solution, 25 ml of the Zr-solution and 650 ml of the respective solution of anunonia in water are mixed.
~rQ~
e~a~p~ 1:
220 cm3 of the actiYated V Ti8 x catalyst were loaded into a tube reactor made of stainless steel (intemal diameter 20 mm, length 1200 rnm).
A gaseous mixture ofthe reagents consisting of 3 ' ,'~,yl;d...., (3-MP), air, ammonia and water vapour was passed through the catalyst layer for 150 hours at a temperature of 385C
with a feeding rate of 103.6 gl-lh-l 3 ~, 27271 I~lh~lair, 113.8gl-1h-1 ammoniaand3364gl~lh~l watervapour.Molarratioofthefeedwas:
The le~ ul c in the reaction zone of the catalyst ranges as a rule between 330C and 440C, preferably between 350C and 410C.
Due to the stable catalyst ~ with respect to life-time, the process according to the present invention can run continously over a long time on a large-scale basis.
he maximum molar yields achievable reach about 95% to 97% for the conversion of 3-c and about 75% for the conversion of 2-methyl-5-cl~J'pJ .; i;"c SUBSTITUTE SHEET (RULE 26~
Wo 9S/32054 2 1 8 8 6 5 5 ~ r ~ ~ fi77 The resulting :yall ~L)yl idill~, i. e. the 3-~yal~ yl idillc and/or the 2,5~ ydl~u~yl idille~ can be directly converted to nicotinic acid by a common hydrolysis trealment ~ith a base.
A nicotinic acid yield of up to 95%. based on 3-methylpyridines, can accordingly be reached.
SUE;STITUTE SHEET (RULE 26) woss/320s4 2 1 8~6 S5 r~ 7, Examples: -catalYst prer,ar~ n a) V Ti8 x catalyst:
690.4 g (3.64 mol) l;l, ,,,.. l,l. ";.l~ is slowly mixed with 400 mi water at a temperature of about 60C to 65C. Water is added to a totai volume of 800 mi.
i n a separate vessel 53 .19 g (0.45 mol) ~,J~Le iS dissolved in 850 mi water and 300 mi of a solution of ammonia in water under ref ux conditions.
During this procedure ammonia is introduced into the solution.
The solution containing the V-compound is added to the Ti-soiution at about 80C to 85C.
Water is added to a total volume of 4 litres.
In a cylinder reactor ~ith mrxing elements 670 mi of the Ti-V-solution having a temperature of 80C to 85C is mixed with 670 mi of a 5.2 % solution of ammonia in water. The wl,- cL;~;l.,le formed is filtered off, washed with water and then dried in an air stream at a temperature of 120C to 140C.
The resulting powder is then treated in a furnace at a temperature of 360C in presence of air over 2 hours, subsequently milled in a ball mill and finaily moistened with water and moulded to tabiets ~ith dimensions 4 x 4 mm. The tablets are treated in a muffe furnace in presence of air at a temperature of 740C for 2 hours.
Fresh prepared catalyst is then activated under oxidative l l~/a;~ conditions with 3-.;Li;.le.
b) V Ti7 5 Zro 5 x cataiyst:
The V-Ti-soiution is prepared as mentioned under a) In a separate vessel 73.27g (0.23 mol) ~IIculllulllo~y~ ' ' ' ' 8 H20 is dissolved in 600 mi of water at tt~ iUl L~ between 40C and 45C.
The w~ L;ull is performed in a Lul ~e~uull i;llg manner as mentioned under a) by mrxing 625 mi of the Ti-V-solution, 100 mi of the Zr-solution and 725 mi of the respective solution of ammonia in water. The further work up of the resulting precipitate is performed as mentioned under a).
V Ti7 5 Zrû 125 Oy catalyst:
SUBSTITUTE SHEET (RULE 26) WO 9~132054 2 1 8 ~ 6 5 S r~ IA7~77 The procedure of example b) was repeated except that for the wp~ d~iU~I 625 ml of the Ti-V-solution, 25 ml of the Zr-solution and 650 ml of the respective solution of anunonia in water are mixed.
~rQ~
e~a~p~ 1:
220 cm3 of the actiYated V Ti8 x catalyst were loaded into a tube reactor made of stainless steel (intemal diameter 20 mm, length 1200 rnm).
A gaseous mixture ofthe reagents consisting of 3 ' ,'~,yl;d...., (3-MP), air, ammonia and water vapour was passed through the catalyst layer for 150 hours at a temperature of 385C
with a feeding rate of 103.6 gl-lh-l 3 ~, 27271 I~lh~lair, 113.8gl-1h-1 ammoniaand3364gl~lh~l watervapour.Molarratioofthefeedwas:
3-~:air(O2):NH3:H2O= 1:22.9:6.0:16.8.
114 g 3-MP waS converted during S hours. The conversion was complete. 119.5 g 3-was obtained ~u,. ~..a~ tO a yield of 93.7% from theory. The output of 3-, ".;i;.,e accordingly was 108 gl-lh-l.
Hydrolysis with KOH (reflux for 2 hours) gave 143.2 g (95% of theory) nicotinic acid.
exam~le 2: - - -The same catalyst as described in example I was used.
A mixture of the reagents cûnsisting of 2-methyl-5-~Lh~ 1~" . ;di~ air. ammonia and water vapour was passed through the catalyst layer at a temperature of 395C. The molar ratio of the feed was:
MEP:air (O2) :NH3 :H2O = 1 :25 :1 9:67. I SS g ~P was converted over I O hours giving 93.2 g 3-."_ rJ.;d;..~.,u"ca~,u,~lil,gtoayieldof70.5%fromtheory.Theouputof3-~,yGIIu~J,;~;,.~, accordingly was 42.8 gl-lh-l Hydrolysis with KOH gave nicotinic acid in a yield of 72% from theory.
example 3: ~ == = = =
The same catalyst (14û cm3) as described in exa~nple I was used.
The same reagents as described in example 2 were passed through the catalyst layer at a temperature of 4ûûC.
SUBSTITUTE SHEET (RULE 26) Wo 9S/32054 ~ 1 8 8 6 5 5 PCT/EP94102677 The molar ratio of the feed was:
MEP:air (O2):NH3:H2O = 1:16:14:30. 53.2 g MEP was converted over S hours giving 19.7 g 2,5-di-,y.ll~ulJylh:l;ll~ (34.8% from theory) and 23.0 g 3-~y~ ùlJyliJ;lle (50 3% from theory).
Hydrolysis with KOH gave nicotinic acid in a yield of 85.4% frûm theory.
L exam~le 4:
lû0 cm3 ûfthe activated V Ti? 5 Zro 5 x catalyst was loaded into the tube reactor mentioned in example 1. A gaseous mixture of 3 ', !~ " ~ (3-MP), air, ammonia and water vapour was passed through the catalyst layer at a temperature of 375C with a feeding rate of 225 gl~ Lh-l 3-MP, 344.1 gl-lh-l air, 111 gl~lh~l NH3 and 980 gl Ih I H2O.
112.3 g 3-MP was converted over S hours giving 92.1 g 3--,yG-lv~), ' (73.2% frûm theory) and 21.8 g, u~ (14.8% from theory).
Hydrolysis with KOH gave 138.7 g (93.3% frûm theory) nictoir~ic acid.
example 5: . -The same catalyst as described in example 4 was applied for a gaseous feed cûntaining MEP
instead of 3-MP The temperature of the catalyst layer was 370C. The feeding rate was:
80 gl-lh-l MEP, 1225 1 air, 180 g NH3 and 1130 g H2O.
48 g MEP was converted over 6 hours giYing 3.6 g 2,5-d;~a..v~J~.iJ;-~e (7% from theory) and 28.9 g 3-.,y~lv,~,~.iui..~, (70% from theory).
Hydrolysis with KOH gave nicûtinic acid in a yield of 79.9% from theûry.
example 6:
100 cm3 of the activated V Ti7 5 Zro 125 x catalyst was applied in the same manner as in example 4. 112.5 g 3-MP was cûnverted over 5 hours giving 100.8 g 3-cyanopyndine (80.1%
from theory) and 17 g nirotin~m~ (11.4% from theory-).
Hydrolysis with KOH gave 139 g (93.3% from theory) nicotinic acid.
example 7 The same catalyst (100 cm3) as described in example I was applied for a gaseous feed containing 3-~Ll.~ . iJi..e (3-EP). The temperature of the catalyst layer was 380C. The feeding rate was: 150 gl-lh-l 3-EP, 36001 I-lh-l air, 167 gl-lh-l NH3 and 252 gl Ih I H2O.
75 g 3-EP was cûnverted over 5 hours giving 66.5 g 3-uy~v~J.id;ll~ (91.2% from theory) example 8:
The same catalyst (100 cm3) as described in example I was applied for a gaseous feed contai-ning 2,5-dimethylpyridine (2,5 DMP). The temperature ofthe catalyst layer was 400C.
The feeding rate was: 102 gl-lh-l 2,5 DMP, 20951 l-lh-l air, 227 gl-lh-l NH3 and650 gl~ I h- I H2O
SUBSTITUTE SHEET (RULE 26 WO 9S/320s4 21 8 8 6 5 5 PCTIEP9~/02677 52 g 2,5 DMP was converted over S hours giving 18.8 g 2,5~ y~l-U~y-;U;lle (30.6% form theory) and 28.8 g 3-~r.llluyJ.;.3;,-c (58.1% frûm theory).
Hydrolysis with NH3 in an autoclave gave nicotinic acid in a yield of 87.9% form theoy.
examt~le 9~
The same cataiyst (lOû cm3) as dçscribed in example I was appiied for a gaseous feed containing 2-methyl-5 .:..,'~,.i i;..c (2-MVP: The temperature ofthe cataiyst was 400C.
The feeding rate was: 113.4 gi-lh-l 2-MVP, 209511-1h-1 air, 227 gi-lh-l NH3 and 750gl-1h-1 H20.
57 g 2-MVp was converted over S hours giving 23.4 g 2,5-d;~ rJ (37 9/~ form theory) and 24.4 g 3-.,y~.u~~ -c (48.9% form theory).
Hydrolysis with NH3 in am autoclave gave nicotinic acid in a yield of 86.3% from theory.
~Y~mnl~ 10. --The same catalyst as described in example I (710 mi) was loaded into a stainiess steel tubereactor (internal diameter 21 mml length 3 m).
A gaseous mixture of the rçagents consisting of 3-~ yl~. i-lL~-c (3-MP), air, ammonia and wat was passed through the cataiyst bed for 1350 hours at a temperature of 385'C with a feedingratewhichvariedbetweenlOOand ~50gl-1h-1 3-~iP,Themolarratioofthefeed3-MP:air(02):ammonia:watervariedbetween 1:5.2:lo:l3and 1:5.2:16:15. 107kg3-MPwas convertedto lO8kg3- ,, ~.r ' Theconversionwas97%.themolaryieldw..t~v~d~,d to 91% and the selectivity 93.5%.
examplç 11: ~
The V Ti8 x catalyst was prepared according to example a), catalyst preparation but with the difference that the heat treatment of the tablets was conducted at a temperature of 850 C
for 2 hours.
140 cm3 of this activated catalyst was loaded into the tube reactor mentioned in example I .
A gaseous mixture of 2-methyl-5-c~l-yl~J.; i;~ll, (MEP), air, ammonia and water vapour was passed thorough the cataiyst layer at a ~tl~ ,.d~UlC of 375 C.
The molar ratio ûf the feed was:
l~p:air(o2):NH3 H2o= l 34:lo:4l s3.2gMEpwasconvertedover5hûursgiving22.8g 2,5-dil,yr..lu~l;Li;,,ec (40.2% from theory) and 22.5 g 3-u.y~llL~/J.;~l;llc (3~.7% from theory).
Hydrolysis with KOH gave nicotinic acid in a yield of 90.2% from theory.
SUBSTITUTE SHEET (RULE 26) ~1\ WO 9~/32054 L ~ ~3 8 6 5 ~ PCTIEP9~/02677 æ
~ O ~ ~
c _ _ u~
.
~ O~ O~
5~ ~ ~
~ ~ ~ OoO 00 æ æ
F G ~ ~ r) ~'I
O l_ 5~ _ ~ O O
~, _ O~ -- ~
Xl ~ ~
.EXI ., 3 , V~
~ G
_ _ _ _ o , G o ~ ~, o ~ ~0 0 ~.
D~ . X ~ ~ ~ ~
G
~UE$TITUTE SHEET (RULE 26~
WO 95132054 2 1 8 8 6 5 5 ~ . ? A77 ~
1 0 _ , ~-- `^ 8 `OD --.
, ~ O ~.
-- ~- ~ ~ O 1~ o~
~ O O O O
E ~ o ~_ ~ _ O~ ~ r-. _ I
;~
.~ E ~ v~ o oo o~
~ ` ~ ~ ~
--- --. ~ _ ~i , o ` ~ o o C~
E ~ oo G
SUBSTITUTE SHEET (RULE 26)
114 g 3-MP waS converted during S hours. The conversion was complete. 119.5 g 3-was obtained ~u,. ~..a~ tO a yield of 93.7% from theory. The output of 3-, ".;i;.,e accordingly was 108 gl-lh-l.
Hydrolysis with KOH (reflux for 2 hours) gave 143.2 g (95% of theory) nicotinic acid.
exam~le 2: - - -The same catalyst as described in example I was used.
A mixture of the reagents cûnsisting of 2-methyl-5-~Lh~ 1~" . ;di~ air. ammonia and water vapour was passed through the catalyst layer at a temperature of 395C. The molar ratio of the feed was:
MEP:air (O2) :NH3 :H2O = 1 :25 :1 9:67. I SS g ~P was converted over I O hours giving 93.2 g 3-."_ rJ.;d;..~.,u"ca~,u,~lil,gtoayieldof70.5%fromtheory.Theouputof3-~,yGIIu~J,;~;,.~, accordingly was 42.8 gl-lh-l Hydrolysis with KOH gave nicotinic acid in a yield of 72% from theory.
example 3: ~ == = = =
The same catalyst (14û cm3) as described in exa~nple I was used.
The same reagents as described in example 2 were passed through the catalyst layer at a temperature of 4ûûC.
SUBSTITUTE SHEET (RULE 26) Wo 9S/32054 ~ 1 8 8 6 5 5 PCT/EP94102677 The molar ratio of the feed was:
MEP:air (O2):NH3:H2O = 1:16:14:30. 53.2 g MEP was converted over S hours giving 19.7 g 2,5-di-,y.ll~ulJylh:l;ll~ (34.8% from theory) and 23.0 g 3-~y~ ùlJyliJ;lle (50 3% from theory).
Hydrolysis with KOH gave nicotinic acid in a yield of 85.4% frûm theory.
L exam~le 4:
lû0 cm3 ûfthe activated V Ti? 5 Zro 5 x catalyst was loaded into the tube reactor mentioned in example 1. A gaseous mixture of 3 ', !~ " ~ (3-MP), air, ammonia and water vapour was passed through the catalyst layer at a temperature of 375C with a feeding rate of 225 gl~ Lh-l 3-MP, 344.1 gl-lh-l air, 111 gl~lh~l NH3 and 980 gl Ih I H2O.
112.3 g 3-MP was converted over S hours giving 92.1 g 3--,yG-lv~), ' (73.2% frûm theory) and 21.8 g, u~ (14.8% from theory).
Hydrolysis with KOH gave 138.7 g (93.3% frûm theory) nictoir~ic acid.
example 5: . -The same catalyst as described in example 4 was applied for a gaseous feed cûntaining MEP
instead of 3-MP The temperature of the catalyst layer was 370C. The feeding rate was:
80 gl-lh-l MEP, 1225 1 air, 180 g NH3 and 1130 g H2O.
48 g MEP was converted over 6 hours giYing 3.6 g 2,5-d;~a..v~J~.iJ;-~e (7% from theory) and 28.9 g 3-.,y~lv,~,~.iui..~, (70% from theory).
Hydrolysis with KOH gave nicûtinic acid in a yield of 79.9% from theûry.
example 6:
100 cm3 of the activated V Ti7 5 Zro 125 x catalyst was applied in the same manner as in example 4. 112.5 g 3-MP was cûnverted over 5 hours giving 100.8 g 3-cyanopyndine (80.1%
from theory) and 17 g nirotin~m~ (11.4% from theory-).
Hydrolysis with KOH gave 139 g (93.3% from theory) nicotinic acid.
example 7 The same catalyst (100 cm3) as described in example I was applied for a gaseous feed containing 3-~Ll.~ . iJi..e (3-EP). The temperature of the catalyst layer was 380C. The feeding rate was: 150 gl-lh-l 3-EP, 36001 I-lh-l air, 167 gl-lh-l NH3 and 252 gl Ih I H2O.
75 g 3-EP was cûnverted over 5 hours giving 66.5 g 3-uy~v~J.id;ll~ (91.2% from theory) example 8:
The same catalyst (100 cm3) as described in example I was applied for a gaseous feed contai-ning 2,5-dimethylpyridine (2,5 DMP). The temperature ofthe catalyst layer was 400C.
The feeding rate was: 102 gl-lh-l 2,5 DMP, 20951 l-lh-l air, 227 gl-lh-l NH3 and650 gl~ I h- I H2O
SUBSTITUTE SHEET (RULE 26 WO 9S/320s4 21 8 8 6 5 5 PCTIEP9~/02677 52 g 2,5 DMP was converted over S hours giving 18.8 g 2,5~ y~l-U~y-;U;lle (30.6% form theory) and 28.8 g 3-~r.llluyJ.;.3;,-c (58.1% frûm theory).
Hydrolysis with NH3 in an autoclave gave nicotinic acid in a yield of 87.9% form theoy.
examt~le 9~
The same cataiyst (lOû cm3) as dçscribed in example I was appiied for a gaseous feed containing 2-methyl-5 .:..,'~,.i i;..c (2-MVP: The temperature ofthe cataiyst was 400C.
The feeding rate was: 113.4 gi-lh-l 2-MVP, 209511-1h-1 air, 227 gi-lh-l NH3 and 750gl-1h-1 H20.
57 g 2-MVp was converted over S hours giving 23.4 g 2,5-d;~ rJ (37 9/~ form theory) and 24.4 g 3-.,y~.u~~ -c (48.9% form theory).
Hydrolysis with NH3 in am autoclave gave nicotinic acid in a yield of 86.3% from theory.
~Y~mnl~ 10. --The same catalyst as described in example I (710 mi) was loaded into a stainiess steel tubereactor (internal diameter 21 mml length 3 m).
A gaseous mixture of the rçagents consisting of 3-~ yl~. i-lL~-c (3-MP), air, ammonia and wat was passed through the cataiyst bed for 1350 hours at a temperature of 385'C with a feedingratewhichvariedbetweenlOOand ~50gl-1h-1 3-~iP,Themolarratioofthefeed3-MP:air(02):ammonia:watervariedbetween 1:5.2:lo:l3and 1:5.2:16:15. 107kg3-MPwas convertedto lO8kg3- ,, ~.r ' Theconversionwas97%.themolaryieldw..t~v~d~,d to 91% and the selectivity 93.5%.
examplç 11: ~
The V Ti8 x catalyst was prepared according to example a), catalyst preparation but with the difference that the heat treatment of the tablets was conducted at a temperature of 850 C
for 2 hours.
140 cm3 of this activated catalyst was loaded into the tube reactor mentioned in example I .
A gaseous mixture of 2-methyl-5-c~l-yl~J.; i;~ll, (MEP), air, ammonia and water vapour was passed thorough the cataiyst layer at a ~tl~ ,.d~UlC of 375 C.
The molar ratio ûf the feed was:
l~p:air(o2):NH3 H2o= l 34:lo:4l s3.2gMEpwasconvertedover5hûursgiving22.8g 2,5-dil,yr..lu~l;Li;,,ec (40.2% from theory) and 22.5 g 3-u.y~llL~/J.;~l;llc (3~.7% from theory).
Hydrolysis with KOH gave nicotinic acid in a yield of 90.2% from theory.
SUBSTITUTE SHEET (RULE 26) ~1\ WO 9~/32054 L ~ ~3 8 6 5 ~ PCTIEP9~/02677 æ
~ O ~ ~
c _ _ u~
.
~ O~ O~
5~ ~ ~
~ ~ ~ OoO 00 æ æ
F G ~ ~ r) ~'I
O l_ 5~ _ ~ O O
~, _ O~ -- ~
Xl ~ ~
.EXI ., 3 , V~
~ G
_ _ _ _ o , G o ~ ~, o ~ ~0 0 ~.
D~ . X ~ ~ ~ ~
G
~UE$TITUTE SHEET (RULE 26~
WO 95132054 2 1 8 8 6 5 5 ~ . ? A77 ~
1 0 _ , ~-- `^ 8 `OD --.
, ~ O ~.
-- ~- ~ ~ O 1~ o~
~ O O O O
E ~ o ~_ ~ _ O~ ~ r-. _ I
;~
.~ E ~ v~ o oo o~
~ ` ~ ~ ~
--- --. ~ _ ~i , o ` ~ o o C~
E ~ oo G
SUBSTITUTE SHEET (RULE 26)
Claims (14)
1. Process for preparing a catalytic composition defined by the formula Va Tib Zrc Ox wherein a is 1 b is 7.5 to 8 c is 0 to 0.5 x represents the number of oxygen atoms necessary to satisfy the valency requirements of the elements present, by coprecipitating a solution of a V5+ -and of a Ti4+- and optionally of a Zr4+-compound in water with a solution of ammonia in water, followed by an exposure of the so-formed precipitate to a drying and heat treatment and by bringing the catalytic compositon in a suitable catalyst form.
2. Process according to claim 1 characterized in that the precipitate formed is either first dried in an air stream at a temperature between 120°C and 140°C, or directly exposed to a heat treatment at temperature between 360°C and 400°C, then shaped into a suitable catalyst form, and finally exposed to a heat treatment at a temperature between 740°C
and 850°C.
and 850°C.
3. Catalytic composition obtainable by the process of claim 1 or 2.
4. Catalytic composition according to claim 3 defined by the formula V Ti8 Ox wherein x is as defined above.
5. Catalytic composition according to claim 3 defined by the formula V Ti7.5 Zr0.5 Ox wherein x is as defined above.
6. Catalytic composition according to claim 3 defined by the formula V Ti7.5 Zr0.125 Ox wherein x is as defined above.
7. Process for the production of cyanopyridines by oxidative ammonolysis of alkylpyridines characterised in that a gaseous feed composed of an alkylpyridine, an oxygen containing gas, ammonia and water vapour is passed over a coprecipitated catalytic composition prepared according to claim 1 at a temperature between 330°C and 440°C.
8. Process according to claim 7 characterised in that a catalytic composition of claim 4 is applied.
9. Process according to claim 7 characterised in that a catalytic composition of claim 5 is applied.
10. Process according to claim 7 characterised in that a catalytic composition of claim 6 is applied.
11. Process according to claim 7 to 10 characterised in that the alkylpyridine is selected from 3-methylpyridine, 3-ethylpyridine, 2-methyl-5-ethylpyridine, 2,5-dimethylpyridine and 2-methyl-5-vinylpyridine.
12. Process according to claim 11 characterised in that 3-methylpyridine or 2-methyl-5-ethylpyridine is selected.
13. Process according to claim 7 to 12 for the production of 3-cyanopyridine by oxidative ammonolysis of 3-methylpyridine characterised in that a gaseous feed of the reactants 3-methylpyridine, oxygen containing gas (calculated to O2), ammonia and water vapour in a molar ratio from 1:7:3:3 to 1:40:10:45 is passed over the catalyst.
14. Process according to claims 7 to 12 for the production of 3-cyanopyridine by oxidative ammonolysis of 2-methyl-5-ethylpyridine characterised in that a gaseous feed of the reactants 2-methyl-5-ethylpyridine, oxygen containing gas (calculated to O2), ammonia and water vapour in a molar ratio from 1:15:5:20 to 1:70:40:140 is passed over the catalyst.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KZ9405601 | 1994-05-23 | ||
KZ940560 | 1994-05-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2188655A1 true CA2188655A1 (en) | 1995-11-30 |
Family
ID=19720744
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002188655A Abandoned CA2188655A1 (en) | 1994-05-23 | 1994-08-11 | Oxidative ammonolysis of alkylpyridines |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0762933A1 (en) |
JP (1) | JP4161119B2 (en) |
KR (1) | KR100331727B1 (en) |
AU (1) | AU7612694A (en) |
BG (1) | BG100989A (en) |
BR (1) | BR9408577A (en) |
CA (1) | CA2188655A1 (en) |
FI (1) | FI964649A (en) |
HU (1) | HUT76437A (en) |
NO (1) | NO964990D0 (en) |
PL (1) | PL317319A1 (en) |
SK (1) | SK149696A3 (en) |
WO (1) | WO1995032054A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2305377A1 (en) | 2009-09-29 | 2011-04-06 | Lonza Ltd. | Catalysts for the preparation of cyanopyridines and their use |
EP2319834A1 (en) * | 2009-10-16 | 2011-05-11 | Lonza Ltd. | Methods and devices for the production of aqueous solutions of cyanopyridines |
EP2428505B1 (en) | 2010-09-13 | 2016-08-10 | Jubilant Life Sciences Limited | Process for producing pyridine carboxylic acids |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2264023B1 (en) * | 1974-03-14 | 1978-09-22 | Showa Denko Kk | |
DE2510994B2 (en) * | 1975-03-13 | 1977-04-14 | Basf Ag, 6700 Ludwigshafen | SUPPORT CATALYST CONTAINING VANADIUM AND TITANIUM |
DE2547655A1 (en) * | 1975-10-24 | 1977-04-28 | Basf Ag | Halo-substd. anthraquinones prepn. - by catalytic oxidn. of diphenyl methane cpds. in gas phase |
ES2026964T3 (en) * | 1987-05-12 | 1992-05-16 | Nippon Shokubai Kagaku Kogyo Co., Ltd | PROCEDURE FOR PRODUCING AROMATIC OR HETERO-CYCLIC NITRILS. |
US5021386A (en) * | 1990-03-21 | 1991-06-04 | Texaco Inc. | Compositions involving V2 O3 -ZRO2 -TIO2 |
-
1994
- 1994-08-11 BR BR9408577A patent/BR9408577A/en not_active Application Discontinuation
- 1994-08-11 HU HU9603235A patent/HUT76437A/en unknown
- 1994-08-11 AU AU76126/94A patent/AU7612694A/en not_active Abandoned
- 1994-08-11 JP JP52999595A patent/JP4161119B2/en not_active Expired - Fee Related
- 1994-08-11 SK SK1496-96A patent/SK149696A3/en unknown
- 1994-08-11 WO PCT/EP1994/002677 patent/WO1995032054A1/en not_active Application Discontinuation
- 1994-08-11 EP EP94926183A patent/EP0762933A1/en not_active Ceased
- 1994-08-11 KR KR1019960706625A patent/KR100331727B1/en not_active IP Right Cessation
- 1994-08-11 PL PL94317319A patent/PL317319A1/en unknown
- 1994-08-11 CA CA002188655A patent/CA2188655A1/en not_active Abandoned
-
1996
- 1996-11-19 BG BG100989A patent/BG100989A/en unknown
- 1996-11-21 FI FI964649A patent/FI964649A/en not_active Application Discontinuation
- 1996-11-22 NO NO964990A patent/NO964990D0/en unknown
Also Published As
Publication number | Publication date |
---|---|
NO964990L (en) | 1996-11-22 |
HUT76437A (en) | 1997-08-28 |
BG100989A (en) | 1997-08-29 |
AU7612694A (en) | 1995-12-18 |
JPH10500892A (en) | 1998-01-27 |
WO1995032054A1 (en) | 1995-11-30 |
NO964990D0 (en) | 1996-11-22 |
FI964649A0 (en) | 1996-11-21 |
FI964649A (en) | 1997-01-21 |
KR100331727B1 (en) | 2002-06-20 |
BR9408577A (en) | 1997-08-19 |
PL317319A1 (en) | 1997-04-01 |
HU9603235D0 (en) | 1997-01-28 |
JP4161119B2 (en) | 2008-10-08 |
EP0762933A1 (en) | 1997-03-19 |
SK149696A3 (en) | 1997-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS6261998A (en) | Amides and teicoplanin compound | |
DE2603698C2 (en) | Method for immobilizing an enzyme on a support | |
DE10261195A1 (en) | Process for the preparation of a symmetrical secondary amine | |
CA2188655A1 (en) | Oxidative ammonolysis of alkylpyridines | |
CN111097468A (en) | Alkyl pyridine ammoxidation catalyst and preparation method thereof | |
SU1189327A3 (en) | Catalyst for producing 3-cyanpyridine | |
JPH08257401A (en) | Catalyst for preparing cyanopyridine,preparation of cyanopyridine and preparation of said catalyst | |
EP0760709B1 (en) | Catalytic composition for the oxidative ammonolysis of alkylpyridines | |
CN107011255B (en) | A kind of method and its purification process preparing aminopyridine by picoline | |
AU2003226632B2 (en) | Ti-pillared clay based vandia catalyst and process for preparation | |
JP2642093B2 (en) | Method for producing 2,4-diamino-5-formylamino-6-hydroxypyrimidine | |
US3970659A (en) | Preparation of cyanopyridines | |
CN106831557A (en) | A kind of method for preparing niacinamide using 3 picolines | |
EP1654233A2 (en) | Method for the manufacture of cyanopyridines and catalysts suitable therefor | |
CN1106314A (en) | Catalyst for preparing cyanopyridine by ammoxidation of alkyl-pyridine and its application | |
Heikens et al. | Polymerization Reactions occurring during Dinitrophenylation of α-, β-and ω-Amino-acids with Sanger's Reagent | |
Marsh et al. | Synthesis of 4-methylumbelliferone β-d-glucuronide, a substrate for the fluorimetric assay of β-glucuronidase | |
CN114426516B (en) | Preparation method of 2-amino-3-bromopyridine | |
BG62760B1 (en) | Catalytic composition for the oxidative ammonolysis of alkylpyridines | |
CN115608355A (en) | Preparation method and application of two-dimensional AuNPs/Ni-TCPP (Fe) nanosheet | |
JPS6368538A (en) | Production of methyl isobutyl ketone | |
CN110483410A (en) | A kind of preparation method of hexahydro-pyridazine dihydrochloride | |
CN109134356A (en) | A kind of preparation method of intermediate 2-amino pyridine -4- methanol | |
JPH0558603A (en) | Production of oxide metal fine powder | |
JP2019202940A (en) | Method for producing compound having six-membered heterocyclic skeleton |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
FZDE | Dead |