1,6- 3,4--2,4--1,6-: , N-

4. .., .., .. // . : - , 2010. 6.1 (12). . 212-213.
5. .., .. 3-(3,3--2-)-3,4--2(1#)- , 1,2- // : . , 3-8 2009 . , 2009. . 288.
547.341+547.725
1,6- 3,4--2,4--1,6-: , N-*
.. , .. , .. , ..
- , .
1,6-DIALKYL SUBSTITUTED 3,4-DIHYDROXY-2,4-HEXADIENE- 1,6-DIONES:
SYNTHESIS, PROPERTIES AND REACTIONS WITH N-DINUCLEOPHILES
^. Karmanova, E.N. Kozminykh, P.P. Mukovoz, V.O. Kozminykh Perm state humanitarian pedagogical university, Perm
1,6--3,4--2,4--1,6-. , - . #- (1,2- 2-) 2,3--(2-)-1,2,3,4- 3-(2-)-3,4--2-1,4-. , .
: , , ---1,3-, 1,6--3,4--2,4--1,6-, , 2,3--(2-)-1,2,3,4-, 1,2-, 2-, 3-(2-)-3,4--2-1,4--2-, 2--2--2-3,4--1,4-, , --.
Claisen condensation of methyl ketones with diethyl oxalate in presence of sodium methylate leads to formation of 1,6-dialkyl-3,4-dihydroxy-2,4-hexadiene-1,6-diones. Seven tautomeric forms are found in solutions of synthesized compounds, ring-chain and ring-ring interconversions are discussed. Condensation of alkyl methyl ketones with diethyl oxalate and #-dinucleophiles (1,2-diaminobenzene and 2-aminophenols) results in 2,3-6/s-(2-oxoalkylidene)-1,2,3,4-tetrahydroquinoxaline and 3-(2-oxoalkilylidene)-3,4-dihydro-2#-1,4-benzoxazine derivatives. With the help of spectral methods several izomeric forms are found, structure peculiarities of synthesized compounds are discussed.
Key words: alkilmetilketony, oksalilnaya condensation disodium bis-dialkyl-1 ,3-diketonates,
1,6-dialkyl-3,4-dihydroxy-2 ,4-hexadiene-1 ,6-diones tautomerism, 2,3-bis (2 oksoalkiliden) -1,2,3,4-tetrahydroquinoxalinyl, 1,2-diaminobenzene, 2-aminophenol, 3 - (2-oksoalkiliden) -3,4-dihydro-2H-1
..., .., .., .., 2013
* .. .
,4-benzoxazin-2-ones 2-alkanoilmetil-2-hydroxy-2H-3,4-dihydro-1,4-benzoxazine, spectral analysis, gas chromatography-mass spectrometry.
, . - , . 1,3,4,6- (), 1,6- .
, , -, , -- -. , , 1,3,4,6- . , 1,6- - - . » , .
- 2--2,3--3-
[1 - 5].
, 1,3-
1,6--3,4--2,4--1,6- 2:1:2 . ---1,3- ^a-). (1f, 1g, 1h, 1k) 1,6- : 1:1:1; , . , (. 1).
(1-) - 1-. - (1-) 1 , , ,
16051655 -1 -
(1) [6]. (1a-k) 1 (87100 %) 1 (0-13 %), 1, ().
, C(2,5)H 1,6- --1,3- 1 5 5,40-5,50 .. 1. C(2,5)H 5 5,82-6,04 .. 1 () [7].

1 1(2

s--s--
.N3

1 1
1
2 2 2
.
N3
- 2 ^
1 1(2)1 1(2)
1 = 12 = (1), 25 (1), -37 (1), - (1d), - (1); 1 = , 12 = 25 (11), 11 = , 12 = - (1g),
11 = 25, 12 = -7 (1h), 11 = 25, 12 = - (1)
1. --- 1,3- (1-)
--1,3- (1)
1
1 2 1, (2,5), .. 1, (2,5), ..
1 5,48 5,86
1 25 25 5,48 5,81
1 - - 5,49 5,90
- - 5,49 5,90
1 -1 -1 - 6,04
1f 3 25 5,49 5,91
1g 3 - 5,43 5,83
1h 25 - 5,52 5,83
1 25 - 5,44 5,82
* ---1,3- (1-) 1 1. (1-) 5 8,34-8,53 .., - - 2. 2 2, , - .

1,3,4,6- (2-). (2-) (1- . (2-) ^ (. 2).


1
1
MeONa 2. 1
1^ ^ + . 1 2
+ * +
II -

1


-1

I!
2
11 (12)
-
' 2


1 1(1 2)'
2 - 2
1
2(1)
1 2
1 = 3, 1 = 2 5 1 2
1 = 3, 1 = 3 7
1 1= 2 5, 1 2= 3 7
1 1= 2 5, 1 2= 511

1 2>^
1 1(1 2)

2 F
12 1 = 2 5, 1 = 3
1 2(1) 1 1=37, 12=3
1 1= 3 7, 1 2= 2 5
12 1 =5 11, 1 = 2 5
11=12=3 (2); 11=12=25 (2); 1=12=-3 (2); 1=12=-5 (2d);
1=12=-13; (2); 11=3, 12=25 (21), 11=3, 12=-3 (2g);Alk1=C2H5, 12=-
37 (2^; 11 = 25, 12=-5 (2)
. 2. 1,6--1,3,4,6- (2-)
1,6--1,3,4,6- (2-) ( ) () 2. 1,6- 1,3,4,6- [8, 9].
1 (2-), , (2,5) 2, - 5 6,33-6,34 ..
( , ) (2-), 1, () () 2, - 2. 2 2 1 (2-) 2, 2, 2, 2F 3% ( 2F ). 2 .
-- (2)
: - 2--4--2- (9), 1,2- - 3--4--3--1,2- (10) (. 3). , (9) (10) .
- 1,6--3,4--2,4--
1,6- (2) .
- 1,6--3,4--2,4--1,6- (2) , - (. 4).
1,6--3,4--2,4--1,6- (2-) . 1 (3)-(4)
2
1 2(11)
. 3 ( - 11(2)+).



11(2) \ . .
+ ^-
MeONa
2 +

1
1
1
1

2
2
11=12=3 (2), 11=12=25 (2), 11=12=-37 (2), 11=12=-511 (2), 11=12=-613 (2), 11=3, 12=25 (21), 11=3, 12=-37 (2g), 11=25, 12=-37 (2). 11=25, 12=-511 (2)
1
1

1

1 =3 (9)
1

1
11=, 2=- (10)
. 3. -- 1,6--3,4--2,4--1,6- (2)



1 2
1 1 1 2 = 3, 25, - 37, - 511, - 613
6 - 100%
4
1+ 1(2) --1-
1/2 - = 1 == | +
0,34 - 1,91%
.
0,04 - 2,32%
3
2-53
- 1
' = 1
6,28 - 15,5%
1(2) 2
2
2-1
1(2) -
1
9 - 54%
+
. 4. - 1,3,4,6-
1,6- 3,4--2,4--1,6- , . - , -, ( - - ).
, 1,3,4,6- , ,
2-6 4
. , () , [10].
6--3,4--6--2,4- () (. 5).
-- 6--3,4--6--2,4- () -1,2,4 (4). , , ( 10°) . , (4) (. 5).
OHO
Ail^V^OMe ^=?TAi^^^AOM<
!- him -
V-
Aik^Me Et(

M
OEt
.
OMe 2
MeONa
+
H
2:l:2
CH5OH


OH
a: Aik =
: Aik = C2H5 : Aik = -C-H
4
4a: Aik = CHj 4b: Aik=h-CjH,
. 5. 6--3,4--6--2,4- (3)
-1,2,4 (4)
1:1:1. [11]. . : , . , .
- (3a, c), , , 3230-3287 -1, 1573 -1 1580 -1, --.
1 (3), , (5 3,80 ..), - . 1 (3-), , (2) C(5)H , - 5 5,95-6,25 .. 5 6,25-6,34 .. . - (3), 1, , (3),
5 11,62-11,63 .., (4), 5 14,65-14,77 ..
- -1,2,4 (4) . - (. 6).

^3
+
- 1
1,71 - 2,13%
\
1
+
^ 100%
7,40 - 12,92%
. 6. - -1,2,4 (4)
-1,2,4 (4) . (^: 85 32+ (4) 113 372+ (4)). (). ^: 126 - + (4) 154 - + (4). 3 ( - 1+) (. . 6).
6--3,4--6--2,4- (3) 1,3,4,6- (2) () . ( 1) , (3) , 1,6--3,4--2,4--1,6- (2), - .
1,3,4,6- .
2,3--(2-)-1,2,3,4- (5^), , 1,6--3,4--2,4--1,6- (2) 1,2- ( ) (. 7). 2:1 1,2-, -() (5) ( ).
(5^) 2,3--= 5, 3100-3400 -1 NH 1705-1737 -1 -. (5^) 5 (86-99%), N#- .

2
1+
-
2,13 - 7,47%

^^- 5 (5 14,03 ..) (5) (4)- 5D (5 14,77 ..) 5 (5 14,72 ..) ( 5g).
, , #- 5D 5, ^1)=(2)- - 5. #- #- .
1 (2)\^
+


^^

11
= 1,
1 NaH (MeONa)


EtOH
^)
2 -
12

^ ^1,
NH2
NH2
^-
' 1,
1 ^ (MeONa) 5 ^
2 1
'
5
NH^
-EtOH
H ^^^11
I "
N.
' ^
12
5
^ ^1,
1
(1 = 3, 2 = C2H5; 1 = 3, 2 = -! 1 = C2H5, 2 = -CH7)
1 = 1 2 = 25 (2, 5); 1 = 12 = -37 (2, 5);
1 = 12 = -511 (2^ 5); 11= 12 = - (2, 5d); 11=, 12 = 25 (2f, 5);
11=, 12 = -37 (2g, 51); 11=25, 12 = -37 (2h, 51).
. 7. 2,3--(2-)-1, 2, 3, 4- (5a-g)
-- 2,3--(2-)-1,2,3,4- (5, d) - 7,9--5-[] (6), (5) (. 8). , (6) .
":
- N + (C9H7N2, m/z = 143)
(C9H8N2, ^ = 144), - 11(2) - (11(2))2+ (m/z = 266)
H +
1
1(2).

2
5
+
(12) (13). (6) *.
- 7,9--5#-[] (6) , - (. 9).
. 8. 7,9--8-[] (6)
1,3,4,6- 1,2- , 2,3--=- 5, 5, ##- . , .
1,6--3,4--2,4--1,6- (2) 2-, (32)-3-(2-)-3,4--2-1,4--2- (7) 2--2--3-(2-)-2-3,4--1,4- (8) (. 10).
(7, d, ) 7, ##- ()
^-"0=. , 1744-1759 -1, NH- 3468-3489 -1 - 3,4--2-1,4--2- (7, d, ). 1 1,4- (7, d, ), , - 5 6,30-6,32 .., 5 6,96-7,56 .. ^4)
1 5 12,1212,48 ..
(), .
1 (8^), , 2 5 2,683,21 .. , 2 (2).
5

CH5 +
13 - 21%

~1+
- Aik 1
100%
.Ak1

- AlkCO] 19 - 90%
2
Aik
21 - 3%


Okl
AlkCO] 5 - 25%
M - 2Alk
21 - 3%
. 9. - (6)
O 1) + 2MeONa O O OH
Alk-> vCH3+ B^OE, 2) + 2HCl , Alk^il''AAlk2 ^ 4lk^vAAik2
O
1) - 2MeOH, - 2EtOH O 2) - 2NaCl
A
O OH
2
B
Aik1 = Aik2 = CH3 (2a), Aik1 = Aik2 = C2H5 (2b), Aik1 = Aik2 = -37 (2c), Aik1 = Aik2 = -C^H^d), Aik1 = Aik2 = -13 (2); Aik1 = C2H5, Aik2 = -37 (2h)
(X = H)
X
"rvAlk+
O^OO
1(2)
X
HO^Alk
lY
1(2)
O^O 1) - MeCOAlk 1(2)
?A 2) - H2O
Alk1=Alk2=CH3 (), C2H5 ^b),
-C3H7 ^c), -C5H11 ^d), -CH13 ()
1(2)
Alk
X
O
O^Alk
OH
O| OHlk2(1) O
- H2O
+
2
S
X = H, Alk1 = Aik2 = -CjH (Sa); X = NO2, Alk1 = Aik2 = -C3H7 (Sb);
X = H, Alk1 = C2H5, Aik2 = -CjH (Sc); X = H, Alk1 = -C3H7, Aik2 = C2H5 (Sd)
. 10. 3,4--2-1,4--2- (, S)
1H (, d, ), -dg, ,19-,20 .. 1H (, d, ) ^4)- 12,19-12,2 .. () -- () ^c), , , .
, . , (la-c, lf, lh, 2, 5) 75 % .
, , , , , . .

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.. // . 2001. . 70. 11. . 10391058.
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