654:
618:
196:
42:
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401:
508:
171:. Some of the most stable diazo compounds are α-diazo-β-diketones and α-diazo-β-diesters, in which the electron density is further delocalized into an electron-withdrawing carbonyl group. In contrast, most diazoalkanes without electron-withdrawing substituents, including diazomethane itself, are explosive. A commercially relevant diazo compound is
360:
324:
757:
The term diazoalkane is used by some authors to refer to any substituted diazomethane (i.e., all diazo compounds). However, other authors use the term to refer exclusively to diazo compounds with alkyl substituents that do not contain other functional groups (which would exclude compounds like
355:
at the terminal nitrogen, proton transfer, and expulsion of the anion of the sulfonamide. Use of the β-carbonyl aldehyde leads to a deformylative variant of the Regitz transfer, which is useful for the preparation of diazo compounds stabilized by only one carbonyl group.
162:
of diazo compounds is characterized by π electron density delocalized over the α-carbon and two nitrogen atoms, along with an orthogonal π system with electron density delocalized over only the terminal nitrogen atoms. Because all
1251:
Hagihara, Ryota; Katsuyama, Yohei; Sugai, Yoshinori; Onaka, Hiroyasu; Ohnishi, Yasuo (2018). "Novel desferrioxamine derivatives synthesized using the secondary metabolism-specific nitrous acid biosynthetic pathway in
997:
Shishkov, I. V.; Rominger, F.; Hofmann, P. (2009). "Remarkably Stable Copper(I) α-Carbonyl
Carbenes: Synthesis, Structure, and Mechanistic Studies of Alkene Cyclopropanation Reactions".
41:
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who had discovered a versatile new chemical reaction, as detailed in his 1858 paper "Preliminary notice on the influence of nitrous acid on aminonitro- and aminodinitrophenol."
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653:
791:
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1196:
970:
Selvaraj, Ramajeyam; Chintala, Srinivasa R.; Taylor, Michael T.; Fox, Joseph M. (2014). "3-Hydroxymethyl-3-phenylcyclopropene".
409:(The mechanism shown here is one possibility. For an alternative mechanism for the analogous formation of diazomethane from an
195:
1189:
532:
605:
320:
is generated in this way by treating methyl phenylacetate with p-acetamidobenzenesulfonyl azide in the presence of base.
167:-satisfying resonance forms of diazo compounds have formal charges, they are members of a class of compounds known as
1297:
1101:
265:
625:
507:
317:
707:-aspartate-nitro-succinate (ANS) pathway. It involves a sequence of enzyme-mediated redox reactions to generate
1302:
804:
277:
633:
1216:
1026:
Strategic
Applications of Named Reactions in Organic Synthesis : Background and Detailed Mechanisms
865:
661:
1151:
Lei, X.; Porco Ja, J. (2006). "Total synthesis of the diazobenzofluorene antibiotic (-)-kinamycin C1".
805:"Vorläufige Notiz über die Einwirkung von salpetriger Säure auf Amidinitro- und Aminitrophenylsäure,"
598:
380:
187:
159:
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by way of a nitrosuccinic acid intermediate. This pathway appears to be active in several different
445:
574:
1095:
586:
498:
1,2-bis(tert-butyldimethylsilyl)hydrazine to form the hydrazone is followed by reaction with the
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172:
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807:(Preliminary notice of the reaction of nitrous acid with picramic acid and aminonitrophenol),
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58:
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compounds, which have the same terminal azo group but bear an overall positive charge, and
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472:
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903:
M. Regitz, Angew. Chem., 79, 786 (1967); Angew. Chem. Intern. Ed. Engl., 6, 733 (1967).
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CHCOOEt). A group of isomeric compounds with only few similar properties are the
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734:
700:
566:
297:
293:
269:
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1072:. Patai, Saul., Wiley InterScience (Online service). Chichester: Wiley. 1978.
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Example: Organic
Syntheses, Coll. Vol. 6, p.981 (1988); Vol. 57, p.95 (1977).
739:
672:
Several families of naturally occurring products feature the diazo group. The
628:, certain diazo compounds react with allyl sulfides to the homoallyl sulfide.
570:
524:
168:
164:
31:
1087:
1043:
983:
937:
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831:
Advanced
Organic Chemistry: Reactions, Mechanisms, and Structure, 3rd edition
391:-nitroso compounds, such as in the synthesis of diazomethane from Diazald or
693:
673:
578:
495:
425:
204:
180:
1277:
1227:
1172:
876:
316:. Examples are the synthesis of tert-butyl diazoacetate and diazomalonate.
17:
491:
70:
708:
590:
562:
414:
352:
1164:
1010:
358:
1138:
Organic
Syntheses, Coll. Vol. 7, p.438 (1990); Vol. 64, p.207 (1986).
1126:
Organic
Syntheses, Coll. Vol. 5, p.258 (1973); Vol. 49, p.22 (1969).
1114:
Organic
Syntheses, Coll. Vol. 6, p.392 (1988); Vol. 50, p.27 (1970).
924:
Organic
Syntheses, Coll. Vol. 6, p.414 (1988); Vol. 59, p.66 (1979).
912:
Organic
Syntheses, Coll. Vol. 5, p.179 (1973); Vol. 48, p.36 (1968).
684:, with diazo functionality as their "warheads". In the presence of a
594:
499:
78:
1238:
Organic Syntheses, Coll. Vol. 6, p.913 (1988); Vol. 50, p.94 (1970).
212:
compounds in which the azo group bridges two organic substituents.
520:
519:
One method is described for the synthesis of diazo compounds from
359:
323:
322:
241:
636:, diazo compounds react with aromatic rings with ring-expansion.
479:
in the synthesis of crotyl diazoacetate and in the synthesis of
392:
1213:
A Phosphine-Mediated Conversion of Azides into Diazo Compounds
268:
using a diazomethyl compound is that of a reaction between an
232:
Several methods exist for the preparation of diazo compounds.
45:
Diazo compounds have two main Lewis structures in resonance: R
648:
yields ketones from aldehydes and aliphatic diazo compounds:
202:
Compounds with the diazo moiety should be distinguished from
40:
183:, where the carbon and two nitrogens are linked as a ring.
790:
Trevor I. Williams, 'Griess, (Johann) Peter (1829–1888)',
30:
For a discussion of copiers using the diazo process, see
312:-toluenesulfonamide). This reaction is also called the
73:
atoms at the terminal position. Overall charge-neutral
1140:
http://www.orgsyn.org/orgsyn/prep.asp?prep=CV7P0438
1070:
The chemistry of diazonium and diazo groups. Part 1
891:, Coll. Vol. 3, p.119 (1955); Vol. 26, p.13 (1946).
630:
Intramolecular reactions of diazocarbonyl compounds
308:. The byproduct is the corresponding tosylamide (
327:Solid state structure of the diazo compound t-BuO
1028:. Czako, Barbara. Burlington: Elsevier Science.
612:to alkenes, again with a carbene intermediate:
502:difluoroiodobenzene yields the diazo compound:
347:. Key distances: C-N = 1.329 Å, N-N = 1.121 Å.
758:diazo(diphenyl)methane or ethyl diazoacetate).
100:. The simplest example of a diazo compound is
593:. Certain diazo compounds can couple to form
475:RRC=N-NHTs are reacted with base for example
240:Alpha-acceptor-substituted primary aliphatic
8:
561:Diazo compounds are used as precursors to
604:Diazo compounds are intermediates in the
1153:Journal of the American Chemical Society
632:provide access to cyclopropanes. In the
549:Diazo compounds react as 1,3-dipoles in
122:
118:
111:
107:
95:
792:Oxford Dictionary of National Biography
770:
750:
220:Diazo compounds were first produced by
1186:Elusive Natural Product Is Synthesized
1093:
646:Buchner-Curtius-Schlotterbeck reaction
551:diazoalkane 1,3-dipolar cycloadditions
379:Diazo compounds can be obtained in an
77:containing the diazo group bound to a
351:The mechanism involves attack of the
7:
1215:Eddie L. Myers and Ronald T. Raines
413:nitrososulfonamide, see the page on
300:in the presence of a weak base like
276:, for example the first step in the
252:(R = COOR, CN, CHO, COR) react with
703:process for diazo formation is the
692:occurs to generate a DNA-cleaving
25:
577:. (In this regard, they resemble
89:and are described by the general
862:New Syntheses of Diazo Compounds
809:Annalen der Chemie und Pharmacie
652:
616:
531:
506:
399:
256:to generate the diazo compound.
194:
1190:Chemical & Engineering News
947:10.1002/047084289X.rn00444.pub2
794:, Oxford University Press, 2004
585:for example in the reaction of
459:. Other oxidizing reagents are
126:) should not be confused with
1:
581:.) As such they are used in
444:for example the synthesis of
721:genes appear widespread in
1319:
779:Advanced Organic Chemistry
266:electrophilic substitution
260:From diazomethyl compounds
29:
27:Chemical group (>C=N=N)
1270:10.1038/s41429-018-0088-1
777:F.A. Carey R.J. Sundberg
565:, which are generated by
318:Methyl phenyldiazoacetate
69:consisting of two linked
984:10.15227/orgsyn.091.0322
606:Bamford–Stevens reaction
34:. For the software, see
1254:Streptomyces davawensis
278:Arndt-Eistert synthesis
1228:10.1002/anie.200804689
1100:: CS1 maint: others (
1024:Kurti, Laszlo (2005).
877:10.1002/anie.200902785
634:Buchner ring expansion
363:
348:
54:
1217:Angew. Chem. Int. Ed.
866:Angew. Chem. Int. Ed.
662:nucleophilic addition
660:The reaction type is
626:Doyle–Kirmse reaction
573:, for example in the
557:As carbene precursors
362:
326:
314:Regitz diazo transfer
44:
803:Peter Griess (1858)
668:Occurrence in nature
599:carbene dimerization
381:elimination reaction
188:resonance structures
160:electronic structure
115:. Diazo compounds (
1159:(46): 14790–14791.
834:, New York: Wiley,
575:Wolff rearrangement
436:) for example with
136:diazonium compounds
1199:2008-08-28 at the
871:, 48, 8186 – 8195
587:ethyl diazoacetate
483:from PhCHNHTs and
481:phenyldiazomethane
375:-nitroso compounds
364:
349:
173:ethyl diazoacetate
91:structural formula
55:
1298:Functional groups
1222:, 48, 2359 –2363
1192:October 31, 2006
1165:10.1021/ja066621v
1079:978-0-470-77154-9
1035:978-0-08-057541-4
1011:10.1021/om8007376
956:978-0-470-84289-8
889:Organic Syntheses
815: : 123-125.
706:
682:DNA intercalation
545:In cycloadditions
465:manganese dioxide
461:lead tetraacetate
457:acetone hydrazone
284:By diazo transfer
264:An example of an
75:organic compounds
59:organic chemistry
16:(Redirected from
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485:sodium methoxide
473:Tosyl hydrazones
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81:atom are called
36:Diazo (software)
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469:Swern reagent
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442:mercury oxide
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678:lomaiviticin
671:
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597:in a formal
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438:silver oxide
424:
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313:
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294:carbon acids
289:
287:
274:diazomethane
263:
254:nitrous acid
239:
231:
222:Peter Griess
219:
209:
203:
201:
185:
157:
102:diazomethane
87:diazoalkanes
86:
82:
62:
56:
1258:J. Antibiot
1188:Stu Borman
735:Reprography
701:biochemical
688:, loss of N
567:thermolysis
515:From azides
449: [
298:tosyl azide
296:react with
270:acyl halide
236:From amines
169:1,3-dipoles
63:diazo group
18:Diazoalkane
1292:Categories
972:Org. Synth
765:References
740:Whiteprint
719:homologous
674:kinamycins
601:reaction.
579:diazirenes
571:photolysis
525:phosphines
426:Hydrazones
181:diazirines
165:octet rule
134:) or with
53:>CH=N=N
32:whiteprint
1096:cite book
1088:501316965
1044:850164343
850:642506595
696:radical.
694:fluorenyl
540:Reactions
496:hydrazine
228:Synthesis
205:diazonium
154:Structure
1278:30120394
1197:Archived
1173:17105273
941:: 1–10.
887:Example
828:(1985),
729:See also
563:carbenes
492:carbonyl
467:and the
430:oxidized
292:certain
71:nitrogen
978:: 322.
709:nitrite
624:In the
595:alkenes
591:styrene
415:Diazald
387:-alkyl-
371:-alkyl-
353:enolate
216:History
132:R−N=N−R
1276:
1171:
1086:
1076:
1042:
1032:
953:
848:
838:
523:using
521:azides
500:iodane
242:amines
79:carbon
67:moiety
61:, the
939:EEROS
746:Notes
589:with
455:from
453:]
367:From
186:Four
98:C=N=N
1274:PMID
1240:Link
1220:2009
1194:Link
1169:PMID
1128:Link
1116:Link
1102:link
1084:OCLC
1074:ISBN
1058:Link
1040:OCLC
1030:ISBN
951:ISBN
926:Link
914:Link
893:Link
869:2009
846:OCLC
836:ISBN
699:One
680:are
676:and
644:The
428:are
393:MNNG
331:CC(N
272:and
244:R-CH
158:The
1266:doi
1256:".
1224:doi
1161:doi
1157:128
1007:doi
980:doi
943:doi
873:doi
813:106
608:of
569:or
440:or
417:.)
383:of
306:DBU
304:or
288:In
248:-NH
210:azo
150:).
140:R−N
121:C=N
85:or
57:In
1294::
1272:.
1262:71
1260:.
1167:.
1155:.
1098:}}
1094:{{
1082:.
1038:.
1003:28
1001:.
976:91
974:.
949:.
844:,
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