394:
361:
20:
321:
408:
425:
455:
ctan-1-yl) which is formed by the action of (3-methyloxetan-3-yl)methanol on activated carboxylic acids in the presence of Lewis acids. The group is base stable and can be cleaved in two steps under mild conditions, mildly acidic hydrolysis yields the ester of tris(hydroxymethyl)ethane which is then
700:
Johnson, William Summer.; Werthemann, Lucius.; Bartlett, William R.; Brocksom, Timothy J.; Li, Tsung-Tee.; Faulkner, D. John.; Petersen, Michael R. (February 1970). "Simple stereoselective version of the
Claisen rearrangement leading to trans-trisubstituted olefinic bonds. Synthesis of squalene".
623:
Houben, J. "Über die
Condensation von Mercaptanen mit Ameisensäure zu Orthotrithio-ameisensäureestern" [On the condensation of mercaptans with formic acid unto formic acid trithio ortho esters].
393:
373:
360:
320:
737:
675:
551:
183:
Although a less common method, ortho esters were first produced by reaction of 1,1,1-trichloroalkanes with sodium alkoxide:
783:
479:
220:
471:
436:
292:
345:
333:
788:
440:
385:
19:
231:
102:
63:
690:
United States Patent
Application 20070049501, Saini; Rajesh K.; and Savery; Karen, March 1, 2007
215:
Compounds with an adjacent hydrogen atom on R tend to undergo elimination instead. Traditional
121:
Upon standing in the presence of excess alcohol, this intermediate converts to the ortho ester:
752:
Hyo Won Lee and
Yoshito Kishi (1985): "Synthesis of mono- and unsymmetrical bis-orthoesters of
105:
in the presence of one equivalent of hydrogen chloride. The reaction proceeds by formation of
733:
671:
575:
547:
28:
761:
710:
655:
641:
633:
605:
539:
460:
377:
223:. The resulting halogenated compounds undergo ether synthesis like the trichloroalkanes.
36:
600:
DeWolfe, Robert H. (March 1974). "Synthesis of carboxylic or carbonic ortho esters".
464:
94:
504:
304:
777:
663:
659:
235:
106:
411:
341:
40:
312:
238:. Traditional transesterification from a cheaper ortho ester is also possible.
543:
152:
Acid chlorides can also drive the reaction from the corresponding amide, e.g.:
475:
415:
252:
149:
The reaction requires anhydrous conditions, and ideally a nonpolar solvent.
59:
55:
637:
227:
62:
and it is from these that the name 'ortho ester' is derived. An example is
443:. Another example is the bicyclic OBO protecting group (4-methyl-2,6,7-tri
407:
609:
381:
308:
226:
Carboxylic acids naturally form a trithio ortho ester when heated with a
765:
714:
311:; and may be further hydrolyzed (under alkaline conditions) to salts of
98:
424:
491:
423:
406:
352:
337:
256:
216:
18:
574:. Organic Chemistry. Vol. 14. New York, NY: Academic Press.
579:
230:
of appropriate stoichiometry. The resulting compound undergoes
538:. PATAI'S Chemistry of Functional Groups. pp. 623–667.
43:
attached to one carbon atom, i.e. with the general formula
534:
E. H. Cordes (1969). "Ortho Esters". In Saul Patai (ed.).
470:(scyllitol) yields the triply-bridged orthoformate esters
54:. Orthoesters may be considered as products of exhaustive
45:
RC(OR<span class="db-bm93cmFw"template-chem2-sub": -->
340:
alcohol with an ortho ester containing a deprotonatable
670:(1st ed.). Oxford University Press. p. 345.
418:, is one of several naturally occurring ortho esters.
219:
can be converted to α,α‑dichloro ethers with
456:cleaved using e.g. an aqueous carbonate solution.
85:, more correctly known as 1,1,1-triethoxyethane.
303:may be hydrolyzed (under acidic conditions) to
234:to a traditional orthoester in the presence of
626:Berichte der Deutschen Chemischen Gesellschaft
435:Examples of orthoesters include the reagents
8:
565:
563:
482:with two fused adamantane-like skeletons.
16:Chemical group with the structure RC(OR')3
431:: 4-methyl-2,6,7-trioxa-bicyclooctan-1-yl
703:Journal of the American Chemical Society
595:
593:
591:
589:
81:
77:
73:
69:
51:
760:, volume 50, issue 22, pages 4402–4404
529:
527:
525:
521:
374:Bodroux–Chichibabin aldehyde synthesis
368:Bodroux–Chichibabin aldehyde synthesis
7:
93:Ortho esters can be prepared by the
23:The general formula of orthoesters.
732:(3. ed.). Stuttgart: Thieme.
14:
572:Carboxylic Ortho Acid Derivatives
570:DeWolfe, Robert H. (1970).
392:
359:
319:
459:The threefold symmetry of the
1:
728:Kocieński, Philip J. (2005).
376:an ortho ester reacts with a
334:Johnson–Claisen rearrangement
328:Johnson–Claisen rearrangement
255:in mild aqueous acid to form
160: + BzCl → HC(OBz)NH
758:Journal of Organic Chemistry
536:Carboxylic Acids and Esters
171:Cl + ROH → HC(OR)
805:
544:10.1002/9780470771099.ch13
480:scyllitol bis-orthoformate
384:; this is an example of a
251:Ortho esters are readily
107:imido ester hydrochloride
638:10.1002/cber.19120450319
221:phosphorus pentachloride
472:scyllitol orthoformate
437:trimethyl orthoformate
432:
419:
336:is the reaction of an
293:trimethyl orthoformate
24:
427:
410:
346:triethyl orthoacetate
60:orthocarboxylic acids
22:
610:10.1055/s-1974-23268
478:-like skeleton, and
441:triethylorthoacetate
386:formylation reaction
766:10.1021/jo00222a046
715:10.1021/ja00706a074
232:transesterification
433:
420:
64:ethyl orthoacetate
25:
784:Functional groups
739:978-3-13-135603-1
730:Protecting groups
677:978-0-19-850346-0
668:Organic Chemistry
658:; Greeves, Nick;
656:Clayden, Jonathan
39:containing three
29:organic chemistry
796:
768:
750:
744:
743:
725:
719:
718:
697:
691:
688:
682:
681:
652:
646:
645:
642:Internet Archive
640:– via the
620:
614:
613:
597:
584:
583:
567:
558:
557:
531:
461:cyclohexanehexol
396:
378:Grignard reagent
363:
351:
323:
286:
282:
266:
210:
202:
198:
194:
136:
132:
128:
116:
84:
49:
37:functional group
804:
803:
799:
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561:
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403:
370:
350:γ,δ-unsaturated
349:
330:
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284:
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274:
270:
264:
249:
244:
208:
206:
200:
196:
192:
190:
179:Cl + BzOH.
178:
174:
170:
163:
159:
144:
140:
134:
130:
126:
114:
95:Pinner reaction
91:
83:
79:
75:
71:
67:
53:
47:
44:
17:
12:
11:
5:
802:
800:
792:
791:
786:
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769:
745:
738:
720:
709:(3): 741–743.
692:
683:
676:
664:Wothers, Peter
660:Warren, Stuart
647:
615:
604:(3): 153–172.
585:
559:
552:
520:
519:
517:
514:
513:
512:
508:
505:Orthocarbonate
502:
499:
495:
487:
484:
422:
421:
402:
399:
398:
397:
369:
366:
365:
364:
329:
326:
325:
324:
315:and methanol.
305:methyl formate
300:
296:
289:
288:
276:
272:
268:
248:
245:
243:
240:
213:
212:
204:
188:
181:
180:
176:
172:
168:
165:
161:
157:
147:
146:
142:
138:
119:
118:
117:OH + HCl → Cl
90:
87:
15:
13:
10:
9:
6:
4:
3:
2:
801:
790:
787:
785:
782:
781:
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767:
763:
759:
755:
749:
746:
741:
735:
731:
724:
721:
716:
712:
708:
704:
696:
693:
687:
684:
679:
673:
669:
665:
661:
657:
651:
648:
643:
639:
635:
632:: 2942–2946.
631:
628:(in German).
627:
619:
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611:
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603:
596:
594:
592:
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586:
581:
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566:
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553:9780470771099
549:
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354:
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314:
310:
306:
294:
291:For example,
262:
261:
260:
258:
254:
246:
241:
239:
237:
236:zinc chloride
233:
229:
224:
222:
218:
186:
185:
184:
166:
155:
154:
153:
150:
124:
123:
122:
112:
111:
110:
108:
104:
100:
96:
88:
86:
65:
61:
57:
42:
41:alkoxy groups
38:
34:
30:
21:
757:
756:-inositol".
753:
748:
729:
723:
706:
702:
695:
686:
667:
650:
629:
625:
618:
601:
571:
535:
465:
458:
452:
448:
444:
434:
428:
412:Hygromycin B
371:
348:) to give a
342:alpha carbon
331:
290:
250:
225:
214:
182:
151:
148:
120:
92:
58:of unstable
32:
26:
789:Orthoesters
380:to form an
313:formic acid
101:react with
97:, in which
33:ortho ester
778:Categories
516:References
476:adamantane
416:antibiotic
253:hydrolyzed
247:Hydrolysis
175: + NH
133:OH → RC(OR
56:alkylation
602:Synthesis
468:-inositol
242:Reactions
228:mercaptan
167:HC(OBz)NH
89:Synthesis
48:em;">′
666:(2001).
580:70-84226
486:See also
474:with an
401:Examples
382:aldehyde
309:methanol
103:alcohols
99:nitriles
507:, C(OR)
494:, C(OR)
463:isomer
372:In the
338:allylic
275:O → RCO
199:→ RC(OR
125:Cl + 2
113:RCN + R
754:scyllo
736:
674:
578:
550:
492:Acetal
466:scyllo
451:icyclo
344:(e.g.
295:CH(OCH
257:esters
217:esters
209:
193:
127:
414:, an
353:ester
283:+ 2 R
263:RC(OR
156:HCONH
72:C(OCH
35:is a
31:, an
734:ISBN
672:ISBN
576:LCCN
548:ISBN
439:and
332:The
307:and
211:NaCl
195:NaOR
191:+ 3
187:RCCl
141:+ NH
46:0.05
762:doi
711:doi
634:doi
606:doi
540:doi
447:xa-
429:OBO
271:+ H
207:+ 3
27:In
780::
707:92
705:.
662:;
630:45
588:^
562:^
546:.
524:^
388:.
355:.
287:OH
259::
164:Cl
145:Cl
109::
76:CH
68:CH
66:,
764::
742:.
717:.
713::
680:.
644:.
636::
612:.
608::
582:.
556:.
542::
511:.
509:4
500:2
498:R
496:2
453:o
449:b
445:o
301:3
299:)
297:3
285:′
281:′
279:R
277:2
273:2
269:3
267:)
265:′
205:3
203:)
201:′
197:′
189:3
177:4
173:3
169:2
162:2
158:2
143:4
139:3
137:)
135:′
131:′
129:R
115:′
82:3
80:)
78:3
74:2
70:3
52:3
50:)
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