[院w"v嘘"ew嘘k"épi"e亥p"8逢嬰e"mj違q"uƒvn "vj運k"ikcp"vj詠e"jk羽p"rj違p"泳pi0Vjgq"f詠"8qƒp. u違p"rj育o"oqpi"ow嘘p"8逢嬰e"j·pj"vj pj"vj»pi"swc"swƒ"vt·pj8„pi"x”pi p瓜k"rj¤p"v穎"e栄c" f磯p"zw医v"rjgp{ncokpq"dgp¦cokfg. Dq"8„"rj違p"泳pi"8逢嬰e"mj違q"uƒv"vtqpi"pj英pi"mjq違pi" vj運k"ikcp"pi逸p"8吋"mk吋o"8鵜pj"ik違"vjw{院v"vt‒p0"Vw{"pjk‒p."vtqpi"j亥w"j院v"eƒe"vj運k"ikcp"vj穎" pijk羽o."mj»pi"ijk"pj壱p"8逢嬰e"v p"jk羽w"e栄c"u違p"rj育o"rj映"x瑛c"m吋"vt‒p"IE0"Ak隠w"8„"e„" 40 68 13 6 0 10 20 30 40 50 60 70 80 Không khí O2 Ar CO2 J k羽 w" uw 医v" I E "*' + O»k"vt逢運pi"rj違p"泳pi
vt·pj"mj穎"vƒej"nq衣k"e栄c"rj泳eej医v"Ew*KKK+fk宇p"tc0"Vjgq"m院v"sw違"mj違q"uƒv"(hình 3.11) rj違p" 泳pi"z違{"tc"t医v"pjcpj"vtqpi"4"ik運"8亥w."ucw"8„"jk羽w"uw医v"v<pi"ej壱o"f亥p"vtqpi"32"ik運"vk院r"
theo. Ucw"34"ik運."jk羽w"uw医v"rj違p"泳pi"vjc{"8鰻k"mj»pi"8ƒpi"m吋0"Ak隠w"p {"e„"vj吋"8逢嬰e"ik違k" vj ej"pj逢"ucw<"vtqpi"ikck"8q衣p"8亥w"e栄c"rj違p"泳pi."khi p欝pi"8瓜"e栄c"eƒe"vƒe"ej医v."z¿e"vƒe" Ew*KK+"x "j o"n逢嬰pi"mj "sw{吋p"qzk"ecq"p‒pvj¿e"8育{swƒ"vt·pj"ejw{吋p"j„c"v衣q"u違p"rj育o" fk宇p"tc"pjcpj0"Ucw"34"ik運."rj違p"泳pi"e„"vj吋"8衣v"8院p"vt衣pi"vjƒk"e¤p"d茨pi."vtqpi"8„"mj違" p<pi"v衣q"rj泳e"e栄c"u違p"rj育o"e„"vj吋"e衣pj"vtcpj"x噂k"piw{‒p"nk羽w0 Dq"8„"8瓜"ejw{吋p"j„c" vjc{"8鰻k"mj»pi"8ƒpi"m吋"x "i亥p"pj逢"d茨pi"pjcw"荏"pj英pi"ik運"m院"vk院r0"A吋"vjw壱p"vk羽p"ejq"
quá trình mj違q"uƒv"e pi"pj逢"8違o"d違q"8吋"8瓜"ejw{吋p"j„c"v嘘v"mjk"vk院p"j pj"eƒe"pijk‒p"e泳w" x隠"違pj"j逢荏pi"e栄c"f磯p"zw医v"u穎"f映pi."vj運k"ikcp"rj違p"泳pi"8逢嬰e"n詠c"ej丑p"n "38"ik運.
Hình 3.11:謂pj"j逢荏ng c栄a th運k"ikcp"8院n hi羽u su医t ph違n 泳ng
3.2 Kh違o sát 違pj"j逢荏ng c栄c"pj„o"8鵜pj"j逢噂ng (2-methyl)thioanilide
Pj„o"8鵜pj"j逢噂pi"e„"xck"vt”"sw{院v"8鵜pj"8院p"mj違"p<pi"j·pj"vj pj"u違p"rj育o"e栄c" rj違p"泳pi0"A吋"mj鰯pi"8鵜pj"v亥o"swcp"vt丑pi"e栄c"pj„o"8鵜pj"j逢噂pi"2-methylthioaniline,
o瓜v"u嘘"pj„o"8鵜pj"j逢噂pi"mjƒe"8«"8逢嬰e"pijk‒p"e泳w"*u挨"8欝 3.12) x噂k"8k隠w"mk羽p"rj違p"泳pi" pj逢"8«"mj違q"uƒv"d‒p"vt‒p0M院v"sw違"ejq"vj医{.":-cokpqswkpqnkpg"dgp¦cokfg"ej雨"v衣q"vj pj" u違p"rj育o"fkog"j„c0"Vtqpi"mjk"8„."o瓜v"pj„o"8鵜pj"j逢噂pi"e„"e医w"vt¿e"v逢挨pi"v詠"n "nhóm (2-fkogvj{ncokpq+cpknkpg"v衣q"8逢嬰e"u違p"rj育o"oqpi"ow嘘p"x噂k"jk羽w"uw医v"x瑛c"rj違k."8衣v" 42%. Eƒe"pj„o"8鵜pj"j逢噂pi"x”pi"7"ej泳c"pkvtqigpe pi"8逢嬰e"mj違q"uƒv."vw{"pjk‒p"mj»pi" 0 10 20 30 40 50 60 70 80 0 2 4 6 8 10 12 14 16 J k羽 w" uw 医v"I E "*' + Vj運k"ikcp"rj違p"泳pi"*ik運+
ijk"pj壱p"8逢嬰e"v p"jk羽w"e栄c"u違p"rj育o"oqpi"ow嘘p0V瑛"8„"mj鰯pi"8鵜pj"8逢嬰e"xck"vt”"swcp" vt丑pi"e栄c"pj„o8鵜pj"j逢噂pi 2-methylthioaniline vtqpi"rj違p"泳pi"p {0
94'"u違p"rj育o"8„pi"x”pi""""""""""mj»pi"v衣q"u違p"rj育o 42'"u違p"rj育o"8„pi"x”pi
Mj»pi"v衣q"u違p"rj育o""""""""""" mj»pi"v衣q"u違p"rj育o
U挨"8欝 3.12:謂pj"j逢荏ng c栄a pj„o"8鵜pj"j逢噂ng. CA = càng c栄a pj„o"8鵜pj"j逢噂ng
3.3 Các d磯n xu医t c栄a N-[2-(methylthio)phenyl]benzamide
X噂k"eƒe"8k隠w"mk羽p"rj違p"泳pi"v嘘k"逢w"8«"v·o"8逢嬰e."eƒe"pj„o"vj院"n亥p"n逢嬰v"8逢嬰e"pijk‒p" e泳w"8吋"mj違q"uƒv"mj違"p<pi"泳pi"f映pi"x "jk羽w"sw違"v鰻pi"j嬰r"e栄c"rj違p"泳pi0
U挨"8欝 3.13:Ak隠u ki羽n ph違n 泳ng phù h嬰r"8«"v·o"8逢嬰c
Cáe"pj„o"vj院"8逢嬰e"e»"n壱r"x "rj¤p"v eje医w"vt¿e"d茨pi"rj鰻"POT"*rj映"n映e A1). A嘘k" x噂k"eƒe"f磯p"zw医v"e栄c"cokfgu"vj·"eƒe"pj„o"vj院"8育{"8k羽p"v穎"ejq"jk羽w"uw医v"ecq"j挨p"uq"x噂k"
vtqpi"8k隠w"mk羽p"v嘘k"逢w"vj·"ijk"pj壱pjk羽w"uw医v"v嘘v n亥p"n逢嬰v"n "92'"x "89'0A員e"dk羽v."mjk" vj詠e"jk羽p"rj違p"泳pi"x噂k"3"ooqn"vƒe"ej医v"ik噂k"j衣p"1a."jk羽w"uw医v"rj違p"泳pi"ik違o"zw嘘pi"e”p" 84'0"Ak隠w"p {"ej泳pi"v臼"vk隠o"p<pi"泳pi"f映pi"rj違p"泳pi荏 quy mô n噂p. Ph違p"泳pi"8衣v"jk羽w" uw医v"ecq"pj医v"n "96' khi có nhóm -CH3 荏"x鵜"vt "meta (3ca)."e„"vj吋8逢嬰e"ik違k"vj ej là do
荏"x鵜"vt "p {pj„o"vj院" v"e違p"vt荏8院pswƒ"vt·pj"jq衣v"j„c"nk‒p"m院v"E&H. Pj„o"vj院"t¿v"8k羽p" v穎"o衣pj"pj逢"hnwqtq"(1d) ejq"8瓜"ejw{吋p"j„c"mjƒ"vj医r."ej雨"8衣v"68'"(3da)0"A吋"mj違q"uƒv" 違pj"j逢荏pi"jk羽w"泳pi"n壱r"vj吋"n‒p"jk羽w"uw医v"rj違p泳pi."eƒe"pj„ovj院e„"m ej"vj逢噂e"n噂p"j挨p" pj逢"rjgpqn"8逢嬰e"d違q"x羽"d茨pi"dgp¦{n (1f), cokpg"d壱e"5"(1g) e pi"8逢嬰e"pijk‒p"e泳w0"M院v" sw違"ejq"vj医{"e違"jck"pj„o8隠w"rj́"j嬰r"x噂k"8k隠w"mk羽p"rj違p"泳pi."ejq"jk羽w"uw医v"n亥p"n逢嬰v"n
53% (3fa) và 50% (3ga)0"A員e"dk羽v"cokfg"e„"e医w"vt¿e"e欝pi"m隠pj"và e嘘"8鵜pj trong không
ikcp"pj逢"pcrjvjcngpg"(1h) x磯p"e„"vj吋"vjco"ikc"rj違p"泳pi."8衣v"jk羽w"uw医v"69'"(3ha). Trong
j亥w"j院v"eƒe"rj違p"泳pi"mj違q"uƒv."u違p"rj育o"cokpg"j„c"mj»pim院v"j嬰r8„pi"x”pip瓜k phân
v穎"8隠w"8逢嬰e"ijk"pj壱p"x噂k"jk羽w"uw医v"vj医r0"Rj違p"泳pi"e pi"8逢嬰e"mj違q"uƒv"x噂k"eƒe"cokfgu" f鵜"x”pi."vw{"pjk‒p"mj»pi"ijk"pj壱p"8逢嬰e"v p"jk羽w"e栄c"u違p"rj育o"ej pj"vt‒p"IE0
B違ng 3.2:Các nhóm th院 c栄a N-[2-(methylthio)phenyl]benzamide
Ak隠w"mk羽p"rj違p"泳pi<"cokfgu"1a-1h (0.1 mmol), aniline 2a (0.2 mmol), Cu(OPiv)2
(0.15 mmol), NaOPiv (0.1 mmol), Cs2CO3 (0.1 mmol), DMSO (1.5 mL), O2."荏"
100oC, trong 16h. [a] 1a (1 mmol).
STT Vƒe"ej医v"3 Vƒe"ej医v" 2 U違p"rj育o Jk羽w"uw医v" e»"n壱r (%) 1 70, 62[a] 2 67 3 74 4 46
5 62
6 53
7 50
8 47
,Jk羽w"uw医v"e»"n壱r"8逢嬰e"v pj"vjgq"vƒe"ej医v"ik噂k"j衣p"N-[2-(methylthio)phenyl]benzamide.
]c̲"Rj違p"泳pi"vj詠e"jk羽p"荏"sw{"o»"3"ooqn"e栄c"piw{‒p"nk羽w"1a.
3.4 Các nhóm th院 c栄a aniline
謂pj"j逢荏pi"e栄c"eƒe"pj„o"vj院"vt‒p"vƒe"ej医v"cpknkpg"e pi"8逢嬰e"swcp"v¤o"vtqpi"pijk‒p" e泳w"p {0"M院v"sw違"v„o"v逸v"8逢嬰e"vt·pj"d {"vtqpi"(d違pi"505) d‒p"f逢噂k0"Vt逢噂e"j院v."eƒe"pj„o" vj院"jcnqigp"i逸p"vt‒p"rj¤p"v穎"cpknkpg"荏"eƒe"x鵜"vt "mjƒe"pjcw"8隠w"ejq"jk羽w"uw医v"rj違p"泳pi" v逢挨pi"8嘘k"ecq"(3ad, 3ae, 3af), 8員e"dk羽v"pj„o"vj院"dtqoo v衣k"x鵜"vt "para ejq"jk羽w"uw医v"ecq" j挨p"8ƒpi"m吋"uq"x噂k"x鵜"vt "ortho. U詠"v衣q"vj pj"eƒe"j嬰r"ej医v"p {"e„"#"pij c"swcp"vt丑pi" vtqpi"xk羽e"8c"f衣pi"j„c"eƒe"f磯p"zw医v"e栄c"u違p"rj育o"ej pj"vj»pi"swc"sw違p"泳pi"vj院"ƒk"pj¤p"
trên nhân vj挨o"jq員e"eƒe"rj違p"泳pi"ijfir"8»k"vj»pi"swc"eqp"8逢運pi"jq衣v"j„c"nk‒p"m院v"
methoxy- (3ab, 3ac) v衣k"x鵜"vt "ortho, meta vt‒p"cpknkpg"e pi"8逢嬰e"mj違q"uƒv"pj茨o"8ƒpj" ikƒ"違pj"j逢荏pi"e栄c"jk羽w"泳pi"8k羽p"v穎"n‒p"8瓜"ejw{吋p"j„c"e栄c"u違p"rj育o0"Vw{"pjk‒p"m院v"sw違 ejq"vj医{."jk羽w"uw医v"rj違p"泳pi"mjk"pj„o"vj院"荏"x鵜"vt "meta ecq"j挨p"pj逢pi"mj»pi"x逢嬰v"vt瓜k" uq"x噂k荏x鵜"vt "ortho. Ngoài tc."pj„o"vj院"p-anisidine và 4-cokpqrjgpqn"e pi"8逢嬰e"mj違q" uƒv"pj逢pi"i亥p"pj逢"mj»pi"ijk"pj壱p"8逢嬰e"u違p"rj育o"oqpi"ow嘘p"n磯p"vƒe"ej医v"vtqpi"j厩p" j嬰r"ucw"rj違p"泳pi0Eƒe"pj„o"t¿v"8k羽p"v穎"o衣pj"pj逢"e{cpq- (3al), trifluoromethoxy- (3ai)
i逸p" v衣k" x鵜" vt "para ejq" 8瓜" ejw{吋p" j„c" v逢挨pi" 8嘘k" ecq. Vw{" pjk‒p" mjk" u穎" f映pi" pj„o"
carboxyl- (3ag) 荏"x鵜"vt para vj·"jk羽w"uw医v"rj違p"泳pi"mjƒ"vj医r, ej雨"8衣v"53' vtqpi"8k隠w" mk羽p"u穎"f映pi"Ew*QCe+2 khan vjc{"vj院"ejq"Ew*QRkx+2. Cu(OAc)2 có jq衣v"v pj"ecq"j挨p
Cu(OPiv)2 pj逢pi"fq"pj衣{"育o"j挨p"p‒p"j衣p"ej院"u穎"f映pi."vtqpi"rj違p"泳pi"x噂k"pj„o"3ag,
e亥p"f́pi"Cu(OAc)2 khan 8吋"ejq"jk羽w"uw医v"ecq"j挨p0"Sw{"vt·pj"ejw育p"d鵜"Cu(OAc)2 khan
n "vj詠e"jk羽pm院v"vkpj"n衣k"ucw"8„"jq衣v"j„c"荏"322oE"d茨pi"Uejngpm"nkpg. F詠cvt‒p"jk羽w"uw医v" e栄c"eƒe"pj„o"vj院"e„"épi"jk羽w"泳pi"8k羽p"v穎"pj逢pi"荏eƒe"x鵜"vt "mjƒe"pjcw"vt‒p"pj¤p"vj挨o" cpknkpg."e„"vj吋"vj医{"jk羽w"泳pi"mj»pi"ikcp 違pj"j逢荏pi"8ƒpi"m吋"8院p"swƒ"vt·pj"ejw{吋p"j„c" j挨p"uq"x噂k"jk羽w"泳pi"8k羽p"v穎0"Ak吋p"j·pj"pj逢"pj„o"vj院"4-cokpqdgp¦cpknkfg"e pi"8逢嬰e" mj違q"uƒv"pj逢pi"jq p"vq p"mj»pi"ijk"pj壱p"8逢嬰e"u詠"ejw{吋p"j„c"e栄c"vƒe"ej医v0"Ak隠w"p {"e„" vj吋"8逢嬰e"ik違k"vj ej"荏"d逢噂e"vtcq"8鰻k"rj嘘k"v穎"x噂k"mko"nq衣k"8欝pi"vtqpi"e挨"ej院"rj違p"泳pi."eƒe" pj„o"vj院"cpknkpg"e„"pj„o"ej泳e"荏"x鵜"vt "ortho e„"vj吋"i¤{"e違p"vt荏"mj»pi"ikcp"mjk"rj嘘k"vt " x噂k"piw{‒p"v穎"8欝pi0"D‒p"e衣pj"8„."pj„o"vj院"j¿v"8k羽p"v穎"vjgq"jk羽w"泳pi"nk‒p"j嬰r"*3ag)
ejq"jk羽w"uw医v"vj医r"j挨p"j鰯p"uq"x噂k"eƒe"pj„o"vj院"ejq"jk羽w"泳pi"e違o"¤o"(3al, 3ai) 荏"épi" x鵜"vt "rctc, ejq"vj医{"v逢挨pi"swcp"x隠"mj違"p<pi"rj嘘k"vt "e栄c"vƒe"ej医v"cpknkpg"v逢挨pi"泳pi"x噂k" piw{‒p" v穎" 8欝pi0" Aƒpi" n逢w" #." eƒe" pj„o" j¿v" 8k羽p" v穎" o衣pj" pj逢" 6-amino-3- nitrobenzonitrile, 2-nitroaniline và 4-pkvtqcpknkpg"e pi"8逢嬰e"mj違q"uƒv"pj逢pi"8隠w"mj»pi" vj詠e"jk羽p"8逢嬰e"ejw{吋p"j„c0 Pj„o"vj院 f鵜"x”pi"ej泳c"pkvtqigp"kokfc¦qnyl (3ak) e pi" 8逢嬰e"pijk‒p"e泳w"pj茨o"8c"f衣pi"j„c"rj衣o"xk"rj違p"泳pi, 8go"n衣k"jk羽w"uw医v"vtwpi"d·pj. Hai
pj„o"vj院"e栄c"4-aminopyridine (2m, 2n) e„"vj吋"8逢嬰e"u穎"f映pi"pj逢"n "pj„o"ej泳e"8鵜pj" j逢噂pi"ejq"rj違p"泳pi"z違{"tc"v衣k"nk‒p"m院v"E-J"荏"x鵜"vt "ortho. Eƒe"pj„o"vj院"f鵜"x”pi"e„"m ej" vj逢噂e" n噂p" pj逢" 5-fluoro-4-morpholinoaniline và 8-aminoquinoline 8隠w" v衣q" 8逢嬰e u違p"
vj院" e栄c" f鵜" x”pi" dgp¦qvjkc¦qng" pj逢" 4-aminobenzothiazole, 2-amino-6- fluorobenzothiazole và 2-amino-6-ogvj{ndgp¦qvjkc¦qng"8隠w"mj»pi"vjco"ikc"rj違p"泳pi0" M院v"sw違"ejq"vj医{."e違"jk羽w"泳pi"8k羽p"v穎"x "jk羽w"泳pi"n壱r"vj吋"8隠w"mj»pi"違pj"j逢荏ng t "t羽v" 8院p"8瓜"ejw{吋p"j„c"e栄c"rj違p"泳pi"p {0Piq k"tc."mjk"u穎"f映pi"e{enqjgz{n"cokpg"vjc{"ejq" cpknkpg"vj·"rj違p"泳pi"ej雨"f瑛pi"n衣k"荏"d逢噂e"8亥w"x噂k"u詠v衣q"vj pj"e栄c"u違p"rj育o amine hóa
mj»pi"8„pi"x”pi8逢嬰e"ijk"pj壱p trên GC-MS.
B違ng 3.3:Các nhóm th院 c栄a aniline
Ak隠w"mk羽p"rj違p"泳pi<"cokfg"1a (0.1 mmol), anilines 2a-2n (0.2 mmol), Cu(OPiv)2
(0.15 mmol), NaOPiv (0.1 mmol), Cs2CO3 (0.1 mmol), DMSO (1.5 mL), O2."荏"
100oC, trong 16h, bu穎"f映pi"Ew*QCe+2*2037"ooqn+"vjc{"vj院"Ew*QRkx+2.
STT Tác ej医v"3 Vƒe"ej医v"4 U違p"rj育o Jk羽w"uw医v"e»" n壱r"*'+
1 68
3 74
4 58
5 53
7 62
8 70
9 57
11 57
12 46
13 40
,Jk羽w"uw医v"e»"n壱r"8逢嬰e"v pj"vjgq"vƒe"ej医v"ik噂k"j衣p"N-[2-(methylthio)phenyl]benzamide