Добавил:
Опубликованный материал нарушает ваши авторские права? Сообщите нам.
Вуз: Предмет: Файл:

Новые достижения в химии и химической технологии растительного сырья. Материалы II всероссийской конференции [2005]

.pdf
Скачиваний:
36
Добавлен:
10.08.2013
Размер:
52.17 Mб
Скачать

! "#$%&'()* +#,&%) -./&0")" #"#012 $&$%#-# 3014&215&- Rhodiola rosea L., -.5)0)"".6 74$%+#481)* 70%-".9 7%#"&0&9 12 4&+")-1( +#$- %)"1': +&21"# (I), +&2#-1"# (II), +&2#+1"# (III) 1 $#015+&215# (IV).

 

OH

 

OH

 

 

 

 

 

 

 

 

O

 

 

O

 

 

 

 

 

 

 

HO

O

HO

O

 

 

HO

 

OH

O

 

OH

 

 

 

 

 

 

HO

O

 

 

I

 

HO

 

 

 

 

OH

 

O O

 

 

 

II

 

 

 

OH

OH

 

OH

O

 

 

 

 

 

 

HO

 

 

O

 

O

 

HO

HO

HO

 

O

OH

OH

 

HO

 

 

 

 

OH

 

 

 

 

 

 

 

III

 

 

IV

:+&-)5)". 1$$0)5&-#"1', "#/+#-0)"".) "# +#2+#,&%4; $/&$&,# /+)/#+#%1-"&3& /&0;<)"1' $#015+&215# (IV) 1 +&2#-1"# (II) 12 74$%+#4- %# +#$%1%)0="&3& $.+=' 9)%&5&9 4&0&"&<"&* 6+&9#%&3+#>11 "124&3& 5#-0)"1'. ?$%#"&-0)"&, <%& 3014&215. II 1 IV - /+)/#+#%1-"& <1$%&9 -15), /+13&5"&9 50' 4#01,+&-41 #"#01%1<)$4&* #//#+#%;+., ;5#)%$' /&0;<1%= 6+&9#%&3+#>1)* "# 4&0&"4), 2#/&0")""&* $&+,)"%&9 «@1#- $&+,» 130 A16B, 3+#51)"%".9 70C1+&-#"1)9 7%10&-.9 $/1+%&9 +#2- 01<"&* 4&"8)"%+#811 7–14%.

?<1%.-#', <%& 81""#9103014&215. '-0'C%$' 6)9#%#4$&"&9)%+1- <)$4191 9#+4)+#91 -15# Rhodiola rosea L., /+)5$%#-0'0&$= 8)0)$&&,- +#2".9 -./&0"1%= 16 <#$%1<".* -$%+)<".* $1"%)2. :&0;$1"%)%1<)- $41) 81""#9103014&215. ")&,6&519. 50' 4#01,+&-41 #"#01%1<)$4&* #//#+#%;+. /+1 #"#012) +#$%1%)0="&3& $.+='. D+&9) %&3&, &"1 9&3;% ,.%= 1$/&0=2&-#". - ,;5;()9 50' <#$%1<"&3& 2#9)()"1' "#%1-".6 3014&215&- +&51&0. $1"%)%1<)$4&* >&+9&*, - >#+9#8)-%1<)$416 /+)- /#+#%#6.

A1"%)2 3014&215&- /+&-&5101 /& $0)5;C()* $6)9):

 

 

OAc

 

OAc

 

O

Ag2CO3

O

O

 

 

OH

+

OAc

OAc

OAc

OAc

OAc

 

OAc

Br

247

!"#$%&'()*+ ,*&-"$*. /0%1/1234 ,-'55 5-*6"&*$ 7 0%$%6"8' 5-"&'71'. 91-'71'-3 5"$':%2234 #"%&*2%2*+ "4/-/71%-*."6/23 ;*.*- 7"-4*8*:%#7*8* 8%1"&/8* (<=>?, @A, BCD), :1" 5".6"$*$" '#1/2"- 6*1E *&%21*:2"#1E 5"$'#*21%1*:%#7*4 ,$*7".*&"6 # 2/1*6238* ,$*7"-

.*&/8* Rhodiola rosea .

<35"$2%2 0*7$ *##$%&"6/2*+, 5".6"$*6F*+ #&%$/1E #$%&'()*% 636"&3:

1.D/.-/G"1/2 #5"#"G 5"$':%2*H 2/1*6234 ,$*7".*&"6 # 5"8")E( "G-/)%22";/."6"+ 4-"8/1",-/;** 2*.7"," &/6$%2*H.

2.!-"/2/$*.*-"6/2 4*8*:%#7*+ #"#1/6 * #1-'71'-/ 63&%$%2234 ,$*7".*&"6.

3.!-"6%&%2 :/#1*:23+ 6#1-%:23+ #*21%. 0*22/8*$,$*7".*&"6 -"&*"$3 -"."6"+.

I/7*8 "G-/."8, -%.'$E1/13 -/G"13 8",'1 #1/1E "#2"6"+ &$H 5"$'- :%2*H ,$*7".*&"6 7"-*:2"," #5*-1/ 8%&*0*2#7"," 2/.2/:%2*H.

!"#$%& '()"#"#"' *'+,-#-".-,

/.$. $0121345

!"#"$"%&"$'$() *+',-"#'./0112) ,1(/0#'(.0. (3. 40#-"5", ,%. 61(/0#'(.0.'$"7, 1, 8,$,', 742012 (69:0$('."1)

E-mail: compounds@intal.uz

J%7/-#16%223% -/#1%2*H * 5"$':/%83% *. 2*4 -/#1*1%$E23% 6%)%- #16/ *.&/62/ *#5"$E.'(1#H &$H $%:%2*H, / 1/7K% # 0%$E( 5-";*$/71*7* 5-/71*:%#7* 6#%4 ./G"$%6/2*+ :%$"6%7/.

@21%-%# 7 5-*-"&238 /$7/$"*&/8, #"&%-K/)*8 6 8"$%7'$% ;-/,- 8%21 4*2"$*.*&*2/, "G'#$"6$%2 *4 63#"7*+ G*"$",*:%#7"+ /71*62"- #1E( [1]. J'5*2*2 "&*2 *. ,$/6234 /$7/$"*&"6 Anabasis aphylla * 2%7"1"-34 6*&"6 Lupinus, 7"1"-3% "G$/&/(1 -/.$*:2"+ G*"$",*:%#7"+ /71*62"#1E( [2, 3].

L$/6"2"*&23% #"%&*2%2*H "&*2 *. #/834 -/#5-"#1-/2%2234 7$/##"6 5-*-"&234 #"%&*2%2*+, "G$/&/()*4 F*-"7*8 #5%71-"8 G*"- $",*:%#7"," &%+#16*H.

248

!"#$#%&' () ($#%&$#* +*$$,* -#).)/#0*12#* 1()314(& 5"#")6- $,7 # 1#$4*4#0*12#7 5")#8()6$,7 &.2&.)#6)( # 9.&()$)#6)(, %):$) -,.) 5"*65).):#4;, 04) 1)0*4&$#* ( )6$)3 %).*2<.* 9.&()$)#6$)/) #

.<5#$#$)()/) '6*" 5)8().#4 5).<0#4; %)6#9#+#")(&$$,* 5")#8()6- $,* 9.&()$)#6)( 1 $)(,%# #$4*"*1$,%# -#).)/#0*12#%# 1()314(&%#.

= +*.;> 5).<0*$#' $)(,7 -#).)/#0*12# &24#($,7 (*?*14( $&%# 5")(*6*$& "*&2+#' 2-/#6")21#-4-.<5#$#.)21#&+*4)9*$)$& 1 6-8&%*?*$- $,%# 8-9)"%#.-1,3--*$8)6#)21&$&%#.

@17)6$,3 2-/#6")21#-4-.<5#$#.)21#&+*4)9*$)$ I -,. 5).<0*$ 6*3- 14(#*% -")%#14)/) .<5#$#$& $& "*8&+*4)9*$)$ ( 5"#1<414(## 1(*:*5")- 2&.*$$)/) 5)4&A& ( 1<7)% 4).<).*. B&.2)$, (IIa)-(IIc) -,.# 5).<0*$, 5"# 2)$6*$1&+## I 1 8-9)"%#.-67-1,3--*$8)6#)21&$&%# ( <1.)(#'7 [4].

CH2Br

 

 

 

HO

OH

 

 

+

C

CH3

K2CO3

N

 

 

O

X

 

 

 

 

CH2O

OH

 

 

N

 

O

O

 

 

 

O (I I a)- (I I c)

 

 

X

 

 

CH2O

O

 

 

 

O

O

 

N O (I I I a)- (I I I c)

CH2O OH

C CH3

NO

(I )

+

 

CHO

 

 

 

O

 

X

O

 

 

 

 

X

 

CH2O

O

 

 

O

O

N

O (I Va)- (I Vc)

 

 

 

(a) X=Cl; (() X=NO2; (1) X=COOH

!).<0*$$,* $&%# 2'-/#6")21#-4'-.<5#$#.)21#7&.2)$)( (IIa)–(IIc) 5"# 2#5'0*$## ( .*6'$)3 <21<1$)3 2#1.)4* #8)%*"#8)(&.# ( 1))4(*414- (<>?#* 9.&(&$)$, (IIIa)–(IIIc).

C 7)6* )2#1.*$#' 7&.2)$)( (IIa)–(IIc) 1 DE=F ( 5"#1<414(## 2&4&.#- 4#0*12#7 2).#0*14( 3)6& )$# .*/2) 5"*("&?&>41' ( 9.&()$, (IVa)–(IVc).

=)14&( # 14")*$#* 1#$4*8#")(&$$,7 1)*6#$*$#3 (I)–(IV) 6)2&8&$, 6&$$,%# G.*%*$4$)/) &$&.#8& # 15*24"&%# 1H-IEJ.

249

!"#$%&'() 1*-+,- ".$/01$102 (IIa)-(IIc) #'.&.1 2'-3*-4'5##6 1()./0&"7 8 .9:("&0 (8 ;,<3-d6) 12,4–13,4 =./. >'.&.16 %('9.%"0:?-

1.24'5##6 #'.78:7@&"7 8 80/$ 5A0'$11.4. "014:$&( 8 9.:$$ ":(9.= #.:$ (12,2–12,8 =./.). ,$&0:$1/0.%"04'5##( .91('5B08(@&"7 8 80/$

"014:$&.8 #'0 5,3–5,4 (2-<*2) 0 4,9-5,0 =./. (4-<*2). C'.=(&0D$"%0$ #'.&.16 5-H 0 7-H 1,3-9$1E./0.%"(1.8.4. F0%:( .91('5B08(@&"7 8 80/$ /59:$&.8 " G<<! 2,0 HF 8 .9:("&0 7,0–8,0 =./.

<#$%&'6 >,- I:(8(1.1.8 (IIIa)–(IIIc) (8 ;,<3-d6) 0=$@& )('(%- &$'0"&0D$"%0$ "041(:6, )0=0D$"%0$ "/8040 %.&.'6) :$B(& 8 .9:("&0

4,2–4,9 0 2,9–3,4 =./.

!"#$%&'() >,- ".$/01$102 (II–IV) #'.&.16 )01.:0E0/01.8.2 "0"&$=6 #'.78:7@&"7 8 .9:("&0 1,0–2,1 =./. (14 *,=,<*2) 0 4,0–4,1 =./.

(2H, =. 3<*2), 2,69 (2H./.*2$ 0 *10$)=10,6 HF.

J(%0= .9'(E.=, 88$/$10$ 8 "."&(8 =.:$%5:6 I:(8(1.0/.8 )01.:0- E0/01.8.4. I'(4=$1&( #.E8.:7$& #.:5D(&? 1.86$ .'0401(:?16$ ".$/0- 1$107 ". "#$F0I0D$"%0=0 I'(4=$1&(=0.

!"#$%'%&

1.<(/6%.8 C.<., C":(1.8 K.C., G5A=5'(/.8 L.G. C:%(:.0/6 )01.:0E0/01.- 8.4. '7/( // K0=07, "&$'$.)0=07, 90.4$1$E. ,., 1975. 292 ".

2.J:$4$1.8 -.J., ;(:0=.8 ;.*., K(0&9($8 K.K., C9/58()(9.8 C.C, M&$107- E.8 G.M. // K0=07 #'0'./16) ".$/01$102. 1990. C. 513.

3.C9/58()(9.8 C.C., J:$4$1.8 -.J., K(09($8 K.K., !(2E95'4 H.N. 0 /'. // K0- =07 #'0'./16) ".$/01$102. 1990. C. 75.

()*+,- N-(!-./+)0)10123*)!) 3*3.3-)*3 ) !/4)*)*3

0.+. +5$6$789

!"#"$"%&"$'$() *+',-"#'./0112) ,1(/0#'(.0. (3. 40#-"5", ,%. 61(/0#'(.0.'$"7, 1, 8,$,', 742012 (69:0$('."1)

E-mail: compounds@intal.uz

C1(9(E01 0 :5#0101, 4:(816$ (:%(:.0/6 '("&$107 Anabasis aphylla ("$=. chenopodiaceae), 1$.9)./0=6$ /:7 "01&$E.8, #.:5D(:0"? 1(=0 0E &$)10D$"%.4. (1(9(E01 "5:?I(&(, #'$/"&(8:7@O$4. "=$"?

250

!"#$%&'() *+!', -(,.(), *,/(-( 0/,1+23+1(4( ) !+#$!-(1 5(637- !')+ ) -&8+!')+ ,2!+-',9,.&.

:,6-(-,03;&3 %/&-9,3 <'(7 !1+!, !(!'(,' ,6 &2&=&6,2& , #"0,- 2,2&. >#3 /&6.+#+2,3 0(!#+.2,5 =?# ,!0(#$6()&2 1+'(. 2,'/(6,/()&- 2,3, 0(6)(#3@;,7 0(#"8,'$ 5/(1&'(4/&%,8+!-, 8,!'?+ &2&=&6,2 , #"0,2,2 [1–3].

A( !)(,1 %&/1&-(#(4,8+!-,1 !)(7!')&1 -(,. &2&=&6,2 ('2(!,'!3 - 4&24#,(2&/2?1 3.&1 , 3)#3+'!3 ',0,82?1 H-5(#,2(1,1+',-(1 [1].

B&=('&1, /3.& ,!!#+.()&'+#+7 0(-&6&2(, 8'( 0/, 6&1+;+2,, )(.(- /(.& 0/, &'(1+ &6('& 0,0+/,.,2()(4( -(#$9& &2&=&6,2& 2& -,#$2?+ /&.,-? 0/(,!5(.,' !2,C+2,+ '(-!,82(!', , 0(3)#+2,+ 2()(7 =,(#(- 4,8+!-(7 &-',)2(!',.

D <'(7 '(8-, 6/+2,3 0/+.!'&)#3+'!3 ,2'+/+!2?1 !,2'+6 N--,# 6&1+;+22?5 0/(,6)(.2?5 &2&=&6,2& , #"0,2,2&:

 

 

 

N

 

N

N

CH2CH2CH2 NCS

N

H + CH2

CH CH2 NCS

CH2OCH2CH2CH2NCS

 

 

 

 

CH2OH

 

 

 

 

 

N

 

N

 

 

D,2'+6 )?*+"-&6&22?5 !(+.,2+2,7 (!";+!')#3#, /&62?1, -(#,- 8+!')&1, #,#/(.&2,.& ) 0/,!"'!'),, -&',6&'(/& (20%, NaOH, KOH) , /&!')(/,'+#+7 0/, 2&4/+)&2,, , =+6 2&4/+)&2,,. E(/(*,+ )?- 5(.? =?#, 0(#"8+2? 0/, -,038+2,, &2&=&6,2& , #"0,2,2& ! ,6=?'-(1 #,#/(.&2,.& ) FGH ) 0/,!"'!'),, 40%-2(4( KOH.

I?5(. 9+#+)?5 0/(."-'() 47–72%.

J2.,),."$2(!'$ !,2'+6,/()&22?5 !(+.,2+2,7 -(2'/(#,/(), '(2-(!#(72(7 5/(1&'(4/&%,+7 0( !,#"%(#+ ) !,!'+1+ 5#(/(%(/1 <'&2(# (2 : 1). K(2+82?+ 0/(."-'? (8,;, 1+'(.(1 -(#(2(82(7 5/(- 1&'(4/&%,, 2& !,#,-&4+#+ L 100\250. D'/(+2,+ 0(#"8+22?5 !(+.,2+- 2,7 .(-&6&2( .&22?1, <#+1+2'2(4( &2,6& , ALB-!0+-'/(!-(0,,.

I ALB !0+-'/&5 0/(,6)(.2(4( &2&=&6,2& ) (=#&!', 8,35; 7,16 , 7,57 1,.. /&!0(#(C+2? !,42? !, ", , #-0/('(2() 0,/,.,2()(4( 9,-#&. D,42&-

251

!" #$%&%'%( #)#*$)+)'%(%,% -).!/ $/0#%!%1*'" ( %2!/0&) 3,05–3,20 3.+. $*4%')$56& #$%&%'" H2! H6!; 0),'/!" H6! $/0#%!%1*'" #$) 2,12 3.+.

7 0!58/* !5#)')'%(%,% #$%)4(%+'%,% 0),'/!" 0%+*$1/&09 ( %2- !/0&) 3,1–3,6 3.+., %&'%09:)*09 . #$%&%'/3 –CH2N ;$/,3*'&/. <)$%-

.)= +52!*& (J=10,6 >-) #$) 2,7–2,9 3.+. %&'%0)&09, . ?.(/&%$)/!@'"3

#$%&%'/3 #$) C2e- ) C10e- A)'%!)4)+)'%(%= 0)0&*3".

B0&/!@'"* #$%&%'" –CH2 A)'%!)4)+)'%(%,% .%!@-/ $/0#%!%1*'"

#$) 1,2–2,0 3.+. C%!%1*')9 +$5,)A 0),'/!%( 4/()09& %& .%'.$*&'%,% &)#/ 4/3*0&)&*!9 ) #%+&(*$1+/6& 0&$5.&5$" 0)'&*4)$%(/''"A 0%*+)'*')=.

D/.)3 %2$/4%3, ((*+*')* ( 0%0&/( 3%!*.5!" /!.)!$%+/')!/ A)'%- !)4)+)'%(%,% ) #)#*$)+)'%(%,% ;$/,3*'&%( #%4(%!9*& #%!58/&@ '%("* %$),)'/!@'"* 0%*+)'*')9, %2!/+/6:)* $/4!)8'%= 2)%!%,)8*0.%= /.- &)('%0&@6.

!"#$%'%&

1.E/+".%( F.E. G)3)9 /!./!%)+%( Anabasis aphylla. D/H.*'&, 1956. 223 c.

2.B$*A%( F.C. G)3)9 /!./!%)+%( $/0&*')= EEEI. J., 1965. E. 46.

3.E/+".%( F.E., F0!/'%( G.F., K5H35$/+%( L.K. F!./!%)+" A)'%!)4)+)'%- (%,% $9+/ // G)3)9, 0&*$*%A)3)9, 2)%,*'*4. J., 1975. 292 0.

()*+,+-.) /-)0-12)(34 (3,-1,+0 !-,)-/3()+!1 3 35+6+-()+!1

+.0. 6&78&9:8

!"#"$%&%'$(%) %*$+%+,+ "'-.*%/0$(") 1%2%% %2. !.!.3"'"45"#. 67 89!, :'. .(.;. <.#'0*+=0#., 9,

!"#"$%&%'$(, 630090 (8"$$%>) E-mail: bakhval@nioch.nsc.ru

I/'** [1–2] '/3) 2"!% #%./4/'%, 8&% )4 %0'%('"A .%3#%'*'&%( 05!@;/&'%,% %8):*''%,% 0.)#)+/$/ (DM 13-4000177-90-85)!-, "-#)- '*'%( ) 3-./$*'/ !*,.% #%!58/*&09 &*A')8*0.)= ')&$/& !-&*$#)'*%!/ (H!T) I. D/.1* !*,.% 3" 0)'&*4)$%(/!) )4 #$%3"H!*''%,% ./3;*'/ (>BED 15039-76) ')&$/& )4%2%$'*%!/ Ia [3]. N%0&5#'%0&@ #*$*8)0!*'- '"A &*$#*'%( ) &*A'%!%,)8'%0&@ #$*($/:*')9 )A ( ')&$/&" 0&)35!)- $%(/!) #%)0. #5&*= #$*($/:*')9 #%0!*+')A ( #%!*4'"* #$%+5.&". B0%2*''% /.&5/!@'/ ?&/ 4/+/8/ +!9 '*50&%=8)(%,% 0%*+)'*')9 I. M0- &%=8)("= ')&$/& Ia #%&*'-)/!@'% 3%1*& )0#%!@4%(/&@09 2*4 ./.%=-

252

!"#$ %"&"'()*$+ $#,-#$.*", .(& /( &(/(( ,-)0",(/"( $#!-)." 1,"&(- /(/"2 3$).41/$5$ /$6$5$ )$(3"/(/"2 6)(53- 7(!-.(!8/$.

9,-/):$,&-;"< 1,$34*.-, )$3(,7-=(5$ 70–80% )$(3"/(/"2 I, $)4=().6!2!" 3(+).6"(& 5"3,->"/5"3,-.- (??) 6 )1",.-%. @A#$, ,-- ;"$/-!8/A% 4)!$6"+ 1,$6(3(/"2 #-!-/)$6$5$ $1A.- 1,$6(!" /- $)/$6( )(,"" B*)1(,"&(/.$6, 1,(3).-6!(//A% 6 .-#!";( 1.

@6"34 3$,$5$6">/A Pd-*-.-!">-.$,- " /(1,$).$5$ (5$ $.3(!(/"2 $. ,(-*;"$//$+ )&()" 6 3-!8/(+0(& ")1$!8>$6-!" #$!(( .(%/$!$5"'- /A( /(*-.-!"."'()*"( 4)!$6"2 ) 1,"&(/(/"(& &(.-/$!-, $#()1('"- 6-<=(5$ #$!(( 6A)$*"+ 6A%$3 $)/$6/A% 1,$34*.$6.

@ #-!-/)$6$& $1A.(, 1,$6(3(//$& 1$ )%(&( (1) ) ")1$!8>$6-/"(& 70%-/$5$ C!9, 6A3(!(/A *$!$/$'/$+ %,$&-.$5,-:"(+ /- )"!"*-5(!( )$(3"/(/"2 II–VII.

 

NH2NH2.H2O

+

+

+

 

CH3OH,52o,2.8!

 

 

 

 

ONO2

 

OCH3

OH

 

 

 

 

 

I

 

II

III

IV

+

+

+

 

(1)

 

 

ONO2

ONO2

 

V

VI

 

VII

 

@A%$3A $. .($,(."'()*$5$ 6 ,-)'(.( /- 100%-/A+ I )$).-6"!" 3!2

II – 26%, III –10%, IV – 29%, V – 14%, VI (#$,/"!/".,-.) – 17%, VII

(!-:(/%"!/".,-.) – 3%. D$(3"/(/"( I 6 1,$34*.-% $.)4.).64(., - /".- ,-.A VI " VII 1(,(%$32., 1$ *,-+/(+ &(,( '-)."'/$, "> ")%$3/$+ 6 *$- /('/4< )&()8.

9-*"& $#,->$&, 6 ,(>4!8.-.( 6$)).-/$6".(!8/$5$ 6$>3(+).6"2 /-

.(%/"'()*"+ C!9 1$!4'-<.)2 1,$34*.A !"#$ ) 47( ">6()./A&" $#!-)-

.2&" 1,"&(/(/"2 (!T " (5$ B:",, 3"1(/.(/), !"#$ 1$3$#/A( ")1$!8- >4(&A& ", )!(3$6-.(!8/$, 1(,)1(*."6/A( (/".,-.A).

253

T!"#$%! 1. &'#()$* $ +,-.#/0!01 )(-2,3'0)$* 44 5! 0,65$7,'8$3 H!T

 

<!'0)(+$-

=(#. (0-

?,;@,+!-

A12,+:8!,

9(2,+:!5$,, % ;!'.*

0,#/

5(>,5$,

0.+!, º9

7

!T**

H!T

BC$+!

 

 

44 : H!T

 

 

 

 

!T

 

 

 

 

 

 

 

 

 

 

 

c 10% Pd/C

 

 

 

 

D0!5(#

1.5

30

1.5

50

16

(0'.

=,0!5(#

1.5

30

1.5

34

(0'.

34

 

 

 

",- 8!0!#$-!0(+!

 

 

 

 

D0!5(#

4.0

60

2.5

40

(0'

'#,21

=,0!5(#

3.0

60

2.5

14

(0'

38

* A ';,'$ (+E!5$7,'8$6 @+(2.80() +,!8%$$. ** !-?,+@$5,(#.

90–95%-513 5$0+!0 Ia @(2),+E!#$ 2,3'0)$F )(''0!5!)#$)!FG$6 !E,50() @( '6,;, (2). ?!"#$%! 2 '(2,+:$0 2!551, @( )!+$!50!; B0(E( @+(%,''! (' $'@(#/-()!5$,; (CH3ONa – ),+65** '0+(8!, ' $'@(#/-()!- 5$,; 5!0+$* 5$:5** '0+(8!).

 

 

 

CH3ONa !"! #$%. Na

 

 

 

 

(2)

 

 

 

 

 

 

 

 

&'(), 2% )*-10

 

 

 

 

 

 

 

ONO2

 

 

 

 

OH

 

 

 

 

 

 

 

 

 

 

 

 

 

 

IIa

Ia

 

 

 

 

 

 

 

H'5()5(, @+,$;.G,'0)( @+,2#!E!,;16 '@('("() '$50,-! $-("(+- 5,(#! @,+,2 @+(;1>#,551; @+(%,''(; ('+.: [4]) – ;*E8$, .'#()$* +,- !8%$$ (0,;@,+!0.+! 35–60 );,'0( 130–160º9, (0'.0'0)$, 2!)#,5$*, @+(- 2(#:$0,#/5('0/ @+(%,''! 1 7 );,'0( 3–8 7).

90+.80.+! '(,2$5,5$3, ("'.:2!)>$6'* ) +!"(0,, .'0!5()#,5! '@,80+!#/51;$ ;,0(2!;$ $ B#,;,5051; !5!#$-(;, (25(+(25('0/ (@+,- 2,#*#!'/ ;,0(2(; 4IJ. A@,+)1, -!@$'!51 '@,80+1 5$0+!0() VI $ VII, ! 0!8:, '@,80+1 K=< 139 '(,2$5,5$3 II $ IV.

?!"#$%! 2.

&'#()$* $ +,-.#/0!01 @+,)+!G,5$* $-("(+5$#5$0+!0! )

 

$-("(+5,(#

 

 

 

 

 

 

 

 

 

 

 

=(#. (05(-

 

L!E+.-8!

?,;@,+!-

A12,+:-

9HA* )

A16(2

>,5$, )('-

 

M=9H, ;#

0.+!, º9

8!, ;$5

(7$G,5-

(7$G,55(-

'0!5()$0,#/ :

 

5! 1 E 5$0-

 

 

5(; @+(-

E( @+(2.8-

5$0+!0

 

+!0!

 

 

2.80,

0!, %* *

8–10

 

9–10

58

50

94

67

6–7

 

8–8.5

35

60

91

60

*9(2,+:!5$, ('5()5(E( ),G,'0)! ) @+(2.80,, (7$G,55(; )(-E(58(3. **100%-5(E( $-("(+5,(#! ) +!'7,0, 5! 100%-513 $-(-"(+5$#5$0+!0.

254

!"#$% &'()$*(%+# ,.-... /.0. 1$%2()+.3 4( 5$6$78 " %(9:+;%$",< 95<,#%$" =>?.

!"#$%'%&

1.!"#$"%&$ '.(., )&*+",-." /.(., 0"1-%&$ 2.(. - 3*. // 4'*5. 2000. 6. 36.

(78. 11. 9. 1648–1653.

2.!"#$"%&$ '.(., !",*:.;<": =.2., 0"1-%&$ 2.(. - 3*. // 4'*5. 2002. 6. 38.

(78. 4. 9. 532–535.

3.!"#$"%&$ '.(., )&*+",-." /.(., =&.> ).0. - 3*. // 4'*5. 1996. 6. 32.

(78. 9. 9. 1358–1362.

4.?@3"<&$ 0.A. 5-B-: - 1>#.&%&,-: <"BC&*7. D., 1976. 9. 93–97.

()*!+,-./)0+1-/)2 /230242!5/67 30+)81+4/67 *-,9+06

1.-. 4:;<=>=?, -... )@%&A"B=?

!"#$%$&$ "'($')%*%% % +,$,-%., /01, 23. 4+$5635, 141,

7(,, 450075 (/8##%5) E-mail: ink@anrb.ru

( 8*>3;1"$%>..&B ;&&EF>.-- 8*-$&3:1;: *>G@%H1"17 -;;%>3&$"-

.-: "$1&*&$ 8& ;-.1>1-+>;<-B 1*".;C&*B"I-:B *"I>B-+>;<&J <"BC&- *7 ; -;8&%HG&$".->B .&$&J *>"<I-- I-<%&B",.-*&$".-: ; 8&B&FHK Et2Mg $ 8*-;@1;1$-- I-*<&.-J;&3>*L"F>,& <"1"%-G"1&*" Cp2ZrCl2. ( <"+>;1$> <%K+>$&,& ;&>3-.>.-: $7E*"%- "%%-%&$7J ;8-*1 (1), ;-.1>- G-*&$"..7J *>"<I->J <"BC&*7 ; "%%-%B",.-J#%&*-3&B.

M;1".&$%>.&, +1& .>8*>3>%H.7J ;8-*1 (1) $;1@8">1 $ *>"<I-K I-<%&B",.-*&$".-: [1] ; -GE71<&B Et2Mg $ ;*>3> 3-N1-%&$&,& NC-*" $ 8*-;@1;1$-- 10 B&%.% <"1"%-G"1&*" Cp2ZrCl2 ; &E*"G&$".->B B",.>G"- I-<%&8>.1"." 2, ;&3>*L"F>,& .&*E&*.".&$7J G"B>;1-1>%H.

O"%-+-> $ B",.>G"I-<%&8>.1".> (2) $7;&<&"<1-$.7# Mg–C ;$:G>J &1<*7$">1 8@1H < ;>%><1-$.&B@ ;-.1>G@ 8*&-G$&3.7# <"BC&*7, " -B>..&, B&.&- (3), 3-- (4) - 1*-&%&$ (5), ;1"E-%H.7# ;-%"I-<%&8>.1"-

.&$ (6), 8*>3;1"$%:KF-# -.1>*>; $ <"+>;1$> <&B8&.>.1&$ 3@P-;17# $>F>;1$.

255

. .

. .

.

 

. .

 

 

.

 

 

.

 

 

O 1. MgCl

 

OH

Et2Mg

OH

 

 

2. H+

 

 

[Zr]

 

Mg

 

 

 

1

 

2

 

R

X [Cu]

[Ni] HCO2Me

O2

R2SiCl2

 

. .

. .

 

 

. .

. .

 

.

.

OH

 

.

.

OH

 

OH

 

OH

OH

 

R

 

 

 

SiR2

 

R

 

OH

 

OH

 

3

4

 

5

 

6

 

R = alkyl, allyl, Ar;[Zr] = Cp ZrCl ; [Cu] = CuCl, CuJ; [Ni] = Ni(acac)

 

 

 

2

2

 

2

 

!"#$%" &'($)*+*" (,- .-*"*/$&$0 ($11+,23+ !$//-0/3$4$ .$*1" .5*- 1"6+*%")7*'8 -//)+1$&"*-0 ((,$+3% 05-03-97905, 9:-2189.2003.3) - ;$*1" /$1+0/%&-< $%+=+/%&+**$0 *"53+.

!"#$%'%&

1.!"#$%' (.)., *+&,-./' 0.)., 1-2$-&3%./' 0.1., 4/&5,%6/' 1.7. // 89' 7: ***0. *#;. <%$. 1991. *. 1388.

()*+,-./0123 4*5/1-56467*8963 861(*0 :+-60)-,125 !/::/9-16(61/

).6. ;'<=>?1, 1./. :&?@%'A"?&2

1!"#"$%&%'$(%) *"$+,-'$.#/001) 2/,-*"*%3/$(%) +0%#/'$%./., 4%56)$(-7, 28, !"#"$%&%'$(, 630126 (8"$$%7)

2!"#"$%&%'$(%) %0$.%.+. "'*-0%3/$(") 9%:%% ;< 8=! %:. !.!. 4"'">?"#-, 2'. -(-,/:%(- @-#'/0.A/#-, 9,

!"#"$%&%'$(, 630090 (8"$$%7) E-Mail pankrush@nioch.nsc.ru

!%,#;=#./'># -&6-&/%3> -6/.%,-./'/?/ ,%=- @'&@A,5@ '#5B$- C#..>$% =;%;/3.>$% 5/#3%.#.%@$%, =/56/&B6+, 5 /3./2 5,/;/.>, /D- &-3-A, '>5/6/2 D%/&/?%E#56/2 -6,%'./5,BA, - 5 3;+?/2 5,/;/.>, $/-

256

Соседние файлы в предмете Процессы и аппараты химических производств