PS_11_KEY - 171d) Problem Set #I | I. Suggested Carey 7th...

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Unformatted text preview: 171d) Problem Set #I | I. Suggested Carey 7th Edition questions: Chapter 22: 22.36; 22.37; 22.44; 22.49 2. Provide the reagents to accomplish the following transformations. More than one step might be required for each transformation. Cl) , alga; MmNgJ DMF @313 LinHq, 5112;) /=-. Q “MW” " (‘0 MW) 14—8149, NEW 4 M5 rm: on. Mp3 “3 LIWUqI 25% IT?) MW .4 MezN W Me»! 2 Br \NHZ OH 2? 0) News, bMF {5) 0mm. €4.20 O OH MezN W MeaN * E Br Ag NH2 /\ 0 Ph t-Bu t-Bu MkBHECN) WK ‘ A“ m, 2% “1w , l a; ”_ . 0 OMG m EMC’U’LWH PhAIgH OMe 5 EtMi—Pr EtAA’PF W S W 1 E E E (ON-Lt; (arm) 3:) ABZD) K190; “MD” ANT; #44 A“; ,. 4 44 Ph N02 j?) MN); x MW; ‘42:?) >‘\ “WOW. A My FaCfijEPh CN {Whom 0"... [42 THC (‘OWE OH mefi‘w - ‘ h emu”, mm; 1 E 1:) EFWIHu,-«£hg , I (ha) K30 5 3. Predict the product for the following transformations. When necessary please explicitly show the F stereochemistry of the product. 1 Me NH2 (i) Mel (excess), THF (ii) A920, H20, MeOH (iii) heat (i) TsCl (4-MeCGH48020I) OH Et3N, CH2Cl2 (ii) NaCN, n-Bu4NBr (cat) THF —_____, (iii) LiAIH4, Et20 (iv) H20 t—Bu (i) HNOs, H2804 Me 0 (ii) Sn, HCi (iii) NaOH, H20 (W) O O JLJL t-BuO o Ot—Bu CH30N (i) NH3, H2, Ni (cat) EtOH 0 (ii) Mel (excess), THF Me (iii) A920, H20, MeOH (iv) heat O (i) piperidine (ii) Mei, THF / l M Gig (iii) H2, Ni (cat) EtOH (IE NaBH3CN, AcOH N H (i) TsCl, EtaN, CHZCI2 OH (ii) NaN3, DMF (iii) LiAlH4, Et20 —> iv) H20 v) Mel (excess), THF vi) A920, H2O, MeOH vii) heat ( E -B tu ( i Et2NH 4/6-“)3 heat aw? «w. Ch --r \ NH2 Brz. Fe(0) -—-———> Me O NH2 (i) Acgo (ii) Br2, Fe(0) U6 K0“. “Va MeO MGUPI’I NH2 (i) NaNog, ACOH (ii) CuCN, heat iii) LiAIH4, Et20 | (i) NaNOZ, ACOH (ii) NaN3 ——> (i) NaNOZ, ACOH (ii) HBF4, heat -—-———-———> (i) NaNOz, ACOH —-—> (i) Fe, HCI (ii) NaOH (iii) NaNOZ, AcOH (iv) CuBr, heat S: (i) Sn, HCI f gm! (ii) NaOH ; __—_—> “ (iii) NaN02, AcOH F No2 (iv) H3P02, heat (i) Fe, HCI u /©\/\/Ph (ii) NaOH ; (iii) NaNOZ, ACOH 0' No2 (iv) CuCI, heat ; (i) H2, Pd/C, EtOH /©:Ph (ii) NaNO2, AcOH —, F N02 (iii) H20, heat Me (i) Sn, HCI (ii) NaOH Q (iii) NaNOZ, ACOH Me NO (W) 2 00M?) (i) Fe, HCI (ii) NaOH 0 N02 (iii) NaN02, AcOH (9033 (iv) ©/NMGZ IO COZH (i) SOCI2, heat (ii) MeNH2 iii) LiAIH4, Et20 I (i) PhCHZNHz (ii) LiAIH4, Et20 (iii) H20 WT; AHA“. fi—“m‘fr 4. Please number the following compounds with the indicated protons in increasing acidity (i.e. | is the least acidic and 4 will be the most acidic.) 6-) 69 ® Ph3N—H thN—H Ph2HN—H PhH2N—H H I \ a C g / N® Et3N—H N—H [ \> g l N H I H i E i i L i 1 542 I0 ‘3’ ‘ “PM 3@ Tl i ' E @,H e H @,H («9 H l H2N HZN/ H2N H2N/ ; N02 @NMG3 H NM92 Li S 2 l l2 5. Perform a retrosynthetic analysis on the following molecules (work backwards) from the given commercially available starting materials. 0 Me 0 Me MeO :> Meo Cl Br lZRLl/UDSKWMQX Q.» W LL. ml ——-——- 0N7 . .— M? i NON w 0 k“ {*3 ~— ill to : El 003‘ 8d” 13 By" L 3 l’lzp r ll Mm V “Ship; \/ MD; as 9mm! a. flag: 0‘1"” ‘ Mk A \ __ “’19 7L“, {5; Mac; «01ng a. Lil wfi 51,1556)“ gown “L H l3 l4 é. Provide a reasonable mechanism to account for the following transformations. When necessary please g explain the observed stereochemistry. é o 0 E 0:: HZNNHZ MHZ NH ' N ———> + . Q EtOH NH N3 0 N3 0 r i C . 1., ® Hoe was heat Me M e MeM/Me M + MeM/ 5 major pdt minor pdt I Please explain the observed regioselectivity of the Hofmann elimination by drawing and analyzing the two transition states leading to the major and minor product. fxuwlwc, N63») MAMA Mmklofibt 3W3 JK'W 71F aivv M “"342 MR “‘1’ M M W30L?Jvl’ my} vg‘ la 5M3 E 3% 5 7i ” “ATVM k RM H—flb MAW ““L W‘Wflwl‘l’g‘w E Coin (“7% l4 E : Me\©\ NaNOz, HCI Me\©\ CUCN M60 1 ____, (+3 ‘ NH2 H20 NSN heat CN Make sure your mechanism accounts for the formation of nitrosyl cation. 5 ‘5’.“2 oh" go fr :0 J 6b/ g /M <5". /N:D wao ~13 + w/ PU? “,9 a? weak E.) 1- ‘J h 0* P j 2’ fl ’4 45>? H T a (7 J] E M. M k” \ v7 CTI @sw flw/M\ Q <—-—~ Blgfi,w==p E MKS—Auk (1% lo \Qh ‘ 575; “42 hAh 9%? “1 MIL-.1 h L1 1; M W <1: 5. M < E a: N ' E3 cN ‘ m C;- W E l5 NMe2 Me H20 NIIN : NMez M M w E]; a} 41 ~ N: QM M % w) 2“ “‘1’ it \ l \ mm W. E E I6 ...
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This note was uploaded on 04/14/2010 for the course ENGL 104 taught by Professor Osbourne during the Spring '08 term at A.T. Still University.

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PS_11_KEY - 171d) Problem Set #I | I. Suggested Carey 7th...

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