848:
1384:, respectively. Most other metals form carbonyls less directly, such as from their oxides or halides. Metal carbonyls are widely employed as catalysts in the hydroformylation and Reppe processes discussed above. Inorganic compounds that contain CO ligands can also undergo decarbonylation, often via a
280:. Many of the commodity carboxylic acids, i.e. propionic, butyric, valeric, etc, as well as many of the commodity alcohols, i.e. propanol, butanol, amyl alcohol, are derived from aldehydes produced by hydroformylation. In this way, hydroformylation is a gateway from alkenes to oxygenates.
267:
565:
358:
834:
715:
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1009:
1172:
1626:
El Ali, B.; Alper, H. "Hydrocarboxylation and hydroesterification reactions catalyzed by transition metal complexes" In
Transition Metals for Organic Synthesis, 2nd ed.; Beller, M., Bolm, C., Eds.; Wiley-VCH:Weinheim, 2004.
150:
111:). Carbonylations are the basis of many types of reactions, including hydroformylation and Reppe reactions. These reactions require metal catalysts, which bind and activate the CO. These processes involve
420:
298:
1507:
Kreis, M.; Palmelund, A.; Bunch, L.; Madsen, R., "A General and
Convenient Method for the Rhodium-Catalyzed Decarbonylation of Aldehydes", Advanced Synthesis & Catalysis 2006, 348, 2148-2154.
738:
604:
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substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to
292:, but many can be induced to do so with appropriate catalysts. A common transformation involves the conversion of aldehydes to alkanes, usually catalyzed by metal complexes:
574:
of methanol is catalyzed by copper(I) salts, which form transient carbonyl complexes. For the oxidative carbonylation of alkenes, palladium complexes are used.
1553:
Takashi Ohara, Takahisa Sato, Noboru
Shimizu, Günter Prescher Helmut Schwind, Otto Weiberg, Klaus Marten, Helmut Greim (2003). "Acrylic Acid and Derivatives".
1524:
Zoeller, J. R.; Agreda, V. H.; Cook, S. L.; Lafferty, N. L.; Polichnowski, S. W.; Pond, D. M. (1992). "Eastman
Chemical Company Acetic Anhydride Process".
1552:
76:
Several industrially useful organic chemicals are prepared by carbonylations, which can be highly selective reactions. Carbonylations produce organic
1555:
1526:
1413:
1588:
262:{\displaystyle {\ce {RCH=CH2 + H2}}+{\color {red}{\ce {CO}}}\longrightarrow {\ce {RCH2CH2}}{\color {red}{\ce {C}}}{\ce {H}}{\color {red}{\ce {O}}}}
1057:
is a special case of hydrocarboxylation reaction that does not rely on metal catalysts. Instead, the process is catalyzed by strong acids such as
1643:
Karlheinz
Miltenberger, "Hydroxycarboxylic Acids, Aliphatic" in Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH: Weinheim, 2003
560:{\displaystyle {\ce {4 CH3OH + O2}}+2\ {\color {red}{\ce {CO}}}\longrightarrow {\ce {2 (CH3O)2}}{\color {red}{\ce {CO}}}+{\ce {2 H2O}}}
1315:
Alkyl, benzyl, vinyl, aryl, and allyl halides can also be carbonylated in the presence carbon monoxide and suitable catalysts such as
353:{\displaystyle {\ce {R}}{\color {red}{\ce {C}}}{\ce {H}}{\color {red}{\ce {O}}}\longrightarrow {\ce {RH}}+{\color {red}{\ce {CO}}}}
829:{\displaystyle {\ce {ArCH(CH3)OH}}+{\color {red}{\ce {CO}}}\longrightarrow {\ce {ArCH(CH3)}}{\color {red}{\ce {CO}}}{\ce {OH}}}
710:{\displaystyle {\ce {RCH=CH2 + H2O}}+{\color {red}{\ce {CO}}}\longrightarrow {\ce {RCH2CH2}}{\color {red}{\ce {CO}}}{\ce {OH}}}
1472:
Beller, Matthias; Cornils, B.; Frohning, C. D.; Kohlpaintner, C. W. (1995). "Progress in hydroformylation and carbonylation".
1690:
1632:
1611:
1300:{\displaystyle {\ce {Me2C=CH2 + H2O}}+{\color {red}{\ce {CO}}}\longrightarrow {\ce {Me3C}}{\color {red}{\ce {CO}}}{\ce {OH}}}
1670:
1572:
1430:
1498:
Hartwig, J. F. Organotransition Metal
Chemistry, from Bonding to Catalysis; University Science Books: New York, 2010.
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1004:{\displaystyle {\ce {C2H4}}+{\color {red}{\ce {CO}}}+{\ce {MeOH -> CH3CH2}}{\color {red}{\ce {CO}}}{\ce {OMe}}}
112:
1167:{\displaystyle {\ce {CH2O}}+{\color {red}{\ce {CO}}}+{\ce {H2O -> HOCH2}}{\color {red}{\ce {CO}}}{\ce {OH}}}
1370:) are prepared by carbonylation of transition metals. Iron and nickel powder react directly with CO to give
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are produced industrially using carbon monoxide and an oxidant, in effect as a source of
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Scott D. Barnicki (2012). "Synthetic
Organic Chemicals". In James A. Kent (ed.).
1069:. The reaction is less applicable to simple alkene. The industrial synthesis of
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Synthesis of acrylic acid using "Reppe chemistry"; a metal catalyst is required.
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1334:, an iron carbonyl complex serves as both metal catalyst and carbonyl source.
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1041:. Under similar conditions, other Pd-diphosphines catalyze formation of
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is like hydrocarboxylation, but it uses alcohols in place of water.
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Riemenschneider, Wilhelm; Bolt, Hermann (2000). "Esters, Organic".
858:
842:
was once mainly prepared by the hydrocarboxylation of acetylene.
380:
273:
137:
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141:
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Elschenbroich, C. ”Organometallics” (2006) Wiley-VCH: Weinheim.
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are the substrates. This method is used industrially to produce
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Few catalysts are highly active or exhibit broad scope.
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Chemical reaction which adds a C=O group onto a molecule
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as intermediates. Much of this theme was developed by
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1604:Handbook of Industrial Chemistry and Biotechnology
1411:W. Bertleff; M. Roeper; X. Sava. "Carbonylation".
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371:Large-scale applications of carbonylation are the
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136:entails the addition of both carbon monoxide and
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1556:Ullmann's Encyclopedia of Industrial Chemistry
1414:Ullmann's Encyclopedia of Industrial Chemistry
1587:: CS1 maint: multiple names: authors list (
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1474:Journal of Molecular Catalysis A: Chemical
892:Methyl propionate ester is a precursor to
728:alcohol is converted to the corresponding
578:Hydrocarboxylation and hydroesterification
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391:is prepared by a related carbonylation of
288:Few organic carbonyls undergo spontaneous
140:to unsaturated organic compounds, usually
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387:. In another major industrial process,
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1606:(12th ed.). New York: Springer.
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144:. The usual products are aldehydes:
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1338:Carbonylation in inorganic chemistry
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276:that bind CO, forming intermediate
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80:, i.e., compounds that contain the
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732:via a Pd-catalyzed carbonylation:
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367:Acetic acid and acetic anhydride
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113:transition metal acyl complexes
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1351:, compounds with the formula
1540:10.1016/0920-5861(92)80188-S
1486:10.1016/1381-1169(95)00130-1
1014:The process is catalyzed by
373:Monsanto acetic acid process
272:The reaction requires metal
7:
10:
1729:
1341:
857:The carbomethoxylation of
126:
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1073:is achieved in this way:
1663:10.1002/14356007.a09_565
1423:10.1002/14356007.a05_217
1559:. Weinheim: Wiley-VCH.
1417:. Weinheim: Wiley-VCH.
1366:(M = metal; L = other
572:oxidative carbonylation
399:Oxidative carbonylation
1513:10.1002/adsc.200600228
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1386:photochemical reaction
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1185:is also illustrative:
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1061:or the combination of
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877:+ CO + MeOH → MeO
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32:Protein carbonylation
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894:methyl methacrylate
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1177:The conversion of
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1583:cite encyclopedia
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98:
90:
86:
79:
69:
67:
63:
59:
55:
51:
47:
43:
42:carbonylation
39:
33:
19:
1681:
1654:
1648:
1639:
1622:
1603:
1597:
1554:
1548:
1531:
1525:
1519:
1503:
1494:
1477:
1473:
1467:
1452:
1441:
1412:
1361:
1355:
1347:
1329:
1314:
1183:pivalic acid
1176:
1052:
1013:
891:
856:
840:Acrylic acid
838:
719:
583:
581:
569:
402:
370:
362:
287:
271:
132:
117:Walter Reppe
75:
41:
35:
1445:Arpe, .J.:
1043:polyketones
385:acetic acid
66:side chains
64:of protein
18:Carbonylate
1702:Categories
1392:References
52:(CO) into
44:refers to
30:See also:
1534:: 73–91.
1480:: 17–85.
1327:powders.
1317:manganese
1263:⟶
1179:isobutene
1134:⟶
958:⟶
784:⟶
722:ibuprofen
663:⟶
481:⟶
331:⟶
274:catalysts
206:⟶
89:aldehydes
78:carbonyls
62:oxidation
58:inorganic
46:reactions
38:chemistry
1020:Pd[C
861:to give
859:ethylene
726:benzylic
381:methanol
138:hydrogen
109:−C(=O)O−
101:−C(=O)OH
87:such as
1368:ligands
1330:In the
588:alkynes
142:alkenes
54:organic
1689:
1669:
1657:: 10.
1631:
1610:
1571:
1459:
1429:
1379:Ni(CO)
1372:Fe(CO)
1325:nickel
1032:PBu-t)
469:
105:esters
103:) and
1353:M(CO)
1323:, or
93:−CH=O
1687:ISBN
1667:ISBN
1629:ISBN
1608:ISBN
1589:link
1569:ISBN
1457:ISBN
1453:2007
1427:ISBN
1377:and
1321:iron
1138:HOCH
1065:and
1053:The
955:MeOH
788:ArCH
744:ArCH
724:, a
570:The
414:.
406:and
375:and
56:and
1659:doi
1561:doi
1536:doi
1509:doi
1482:doi
1478:104
1419:doi
1181:to
1028:(CH
998:OMe
668:RCH
610:RCH
582:In
395:.
383:to
211:RCH
156:RCH
95:),
82:C=O
36:In
1704::
1665:.
1585:}}
1581:{{
1567:.
1532:13
1530:.
1476:.
1451:,
1425:.
1399:^
1388:.
1319:,
1294:OH
1287:CO
1268:Me
1257:CO
1219:CH
1198:Me
1161:OH
1154:CO
1108:CO
1086:CH
1045:.
1018:,
991:CO
975:CH
962:CH
945:CO
896:.
881:CC
865::
823:OH
816:CO
796:CH
778:CO
768:OH
752:CH
704:OH
697:CO
681:CH
657:CO
619:CH
527:CO
495:CH
475:CO
443:OH
431:CH
412:CO
345:CO
335:RH
224:CH
200:CO
165:CH
119:.
68:.
40:,
1675:.
1661::
1616:.
1591:)
1577:.
1563::
1542:.
1538::
1511::
1488:.
1484::
1435:.
1421::
1381:4
1374:5
1362:y
1359:L
1356:x
1280:C
1272:3
1251:+
1247:O
1239:2
1235:H
1231:+
1223:2
1214:=
1210:C
1202:2
1142:2
1131:O
1123:2
1119:H
1114:+
1102:+
1098:O
1090:2
1038:2
1036:]
1034:2
1030:2
1026:4
1024:H
1022:6
979:2
966:3
951:+
939:+
930:4
926:H
917:2
913:C
887:5
885:H
883:2
879:2
875:4
873:H
871:2
869:C
808:)
800:3
792:(
772:+
764:)
756:3
748:(
685:2
672:2
651:+
647:O
639:2
635:H
631:+
623:2
614:=
554:O
546:2
542:H
537:2
533:+
515:2
510:)
507:O
499:3
491:(
485:2
466:2
463:+
454:2
450:O
446:+
435:3
426:4
339:+
325:O
318:H
311:C
304:R
254:O
247:H
240:C
228:2
215:2
194:+
185:2
181:H
177:+
169:2
160:=
107:(
99:(
91:(
20:)
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