CN1216030C - O－酰基－α－羟基羧酸酯类化合物及其制备方法 - Google Patents

O－酰基－α－羟基羧酸酯类化合物及其制备方法 Download PDF

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CN1216030C
CN1216030C CN00101949.XA CN00101949A CN1216030C CN 1216030 C CN1216030 C CN 1216030C CN 00101949 A CN00101949 A CN 00101949A CN 1216030 C CN1216030 C CN 1216030C
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R·费希尔
T·布雷特施奈德
B·-W·克吕格
H·-J·桑特尔
M·多林格
U·瓦兴多夫-努曼
C·艾尔德伦
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract

本发明涉及通式(II)的O-酰基-α-羟基羧酸酯类化合物，A、B、X、Y、Z和n的定义如说明书中所述。本发明还涉及式(II)化合物的制备方法。

Description

O-酰基-α-羟基羧酸酯类化合物及其制备方法
本申请是申请号为94115915.9、申请日为1994年9月16日、发明名称为“3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物”的发明专利申请的分案申请。
本发明涉及新的3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物，其制备方法及其作为农药的用途。
已报道某些被取代的Δ3-二氢呋喃-2-酮衍生物具有除草性能(参见DE-A 4014420)。DE-A 4014420还说明了用作原料化合物的特窗酸衍生物(如3-(2-甲基苯基)-4-羟基-5-(4-氟苯基)-Δ3-二氢呋喃-2-酮)的合成方法。具有类似结构的化合物还已见于Campbell et al.，J.Chem.Soc.，Perkin Trans.1(1985)，(8)1567-76。但并没有报道杀虫和/或杀螨活性。此外，EP528156公开了具有除草、杀螨和杀虫性能的3-芳基-Δ3-二氢呋喃酮衍生物，但其中谈到的活性并不总是足够的。
现已发现式(I)新的3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物及其立体异构和对映异构纯的化合物：
Figure C0010194900041
其中X代表烷基，卤素，烷氧基或卤代烷基，
Y代表氢，烷基，卤素，烷氧基或卤代烷基，
Z代表烷基，卤素或烷氧基，
n代表0-3的数，
或其中X和Z与其连接的苯基一起形成下式的萘基：
Figure C0010194900051
其中Y定义同上，
G代表氢(a)或下列各式的基团：
-CO-R1，(b) -SO2-R3  (d)
Figure C0010194900053
或E  (g)
A和B与其连接的碳原子一起形成被烷氧基，烷硫基，烷基亚磺酰基，烷基磺酰基，羧基或CO2R2取代的环，或
A和B与其连接的碳原子一起代表环，该环中两个取代基与其连接的碳原子一起代表饱和环，而该饱和环可任选被烷基，烷氧基或卤素取代并且可被氧或硫间断，
E代表当量金属离子或铵离子，
L和M各自代表氧或硫，
R1代表在每一情况下均可任选被取代的烷基，烯基，烷氧基烷基，烷硫基烷基，多烷氧基烷基或可被至少一个杂原子间断的环烷基，每一情况下均可任选被取代的苯基，苯基烷基，杂芳基，苯氧基烷基或杂芳氧基烷基，以及
R2代表烷基，环烷基，烯基，烷氧基烷基或多烷氧基烷基，其中每一基团均可任选被取代，或代表每一情况下均可任选被取代的苯基或苄基，
R3，R4和R5相互独立地代表烷基，烷氧基，烷基氨基，二烷基氨基，烷硫基，烯硫基，炔硫基或环烷硫基，其中每一基团均可任选被卤素取代，以及每一情况下均可任选被取代的苯基，苯氧基或苯硫基，
R6和R7相互独立地代表氢，或代表烷基，烯基，烷氧基或烷氧基烷基，其中每一基团均可任选被卤素取代，任选被取代的苯基，任选被取代的苄基，或
R6和R7一起代表可任选被氧或硫间断的亚烷基。
考虑到通式(I)中基团G的各定义(a)，(b)，(c)，(d)，(e)，(f)和(g)，可构成以下主要的结构(Ia)至(Ig)：
Figure C0010194900061
Figure C0010194900071
其中A，B，E，L，M，X，Y，Z，R1，R2，R3，R4，R5，R6，R7和n定义同上。
(A)
而且，还发现式(Ia)的3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物可在稀释剂和碱存在下用式(II)羧酸酯进行分子内缩合反应而得到：
其中A，B，X，Y，Z和n定义同上，
Figure C0010194900082
其中A，B，X，Y，Z和n定义同上，
R8代表烷基。
(B)
而且，还已发现式(Ib)化合物可用式(Ia)化合物得到：
其中A，B，X，Y，Z，R1和n定义同上，
Figure C0010194900091
其中A，B，X，Y，Z和n定义同上，其中：
α)合适时在稀释剂和酸结合剂存在下将式(Ia)化合物与通式(III)的酰卤反应：
其中R1定义同上，
Hal代表卤素，尤其是氯或溴，或
β)合适时在稀释剂和酸结合剂存在下将式(Ia)化合物与通式(IV)的羧酸酐反应：
           R1-CO-O-CO-R1         (IV)
其中R1定义同上。
(C)
而且，还已发现式(Ic)化合物可在合适时在稀释剂和酸结合剂存在下将式(Ia)化合物与通式(V)的氯甲酸酯或硫代氯甲酸酯反应而得到：
其中A，B，X，Y，Z，R2和n定义同上，
L代表氧，
M代表氧或硫，
Figure C0010194900101
其中A，B，X，Y，Z和n定义同上，
                R2-M-CO-Cl           (V)
其中R2和M定义同上。
(D)
而且，还已发现式(Ic)化合物可在合适时在稀释剂和酸结合剂存在下将式(Ia)化合物与通式(VI)的一硫代氯甲酸酯或二硫代氯甲酸酯反应而得到：
Figure C0010194900102
其中A，B，R2，X，Y，Z和n定义同上，
L代表硫，
M代表氧或硫，
Figure C0010194900103
其中A，B，X，Y，Z和n定义同上，
Figure C0010194900111
其中M和R2定义同上。
(E)
而且，还已发现式(Id)化合物可在合适时在稀释剂和酸结合剂存在下将式(Ia)化合物与通式(VII)的磺酰氯反应而得到：
Figure C0010194900112
其中A，B，X，Y，Z，R3和n定义同上，
Figure C0010194900113
其中A，B，X，Y，Z和n定义同上，
                   R3-SO2-Cl          (VII)
其中R3定义同上。
(F)
而且，还已发现式(Ie)化合物可在合适时在稀释剂和酸结合剂存在下将式(Ia)化合物与通式(VIII)的磷化合物反应而得到：
其中A，B，L，X，Y，Z，R4，R5和n定义同上，
其中A，B，X，Y，Z和n定义同上，
Figure C0010194900123
其中L，R4和R5定义同上，
Hal代表卤素，尤其是氯或溴。
(G)
而且，还已发现式(If)化合物可用式(Ia)化合物得到：
Figure C0010194900124
其中A，B，L，X，Y，Z，R6，R7和n定义同上，
其中A，B，X，Y，Z和n定义同上，其中：
α)合适时在稀释剂和催化剂存在下将式(Ia)化合物与通式(IX)的异氰酸酯反应：
                 R6-N＝C＝L        (IX)
其中L和R6定义同上，或
β)合适时在稀释剂和酸结合剂存在下将式(Ia)化合物与通式(X)的氨基甲酰氯或硫代氨基甲酰氯反应：
Figure C0010194900132
其中L，R6和R7定义同上。
(H)
而且，还已发现式(Ig)化合物可在合适时在稀释剂存在下将式(Ia)化合物与通式(XI)和(XII)的金属化合物或胺反应而得到：
Figure C0010194900141
其中X，Y，Z，A，B和n定义同上，
E代表当量金属离子或铵离子，
其中X，Y，Z，A，B和n定义同上，
MeR9 t    (XI)
Figure C0010194900143
其中Me代表一或二价金属离子，
t代表数值1或2，
R9代表氢，羟基或烷氧基，
R10，R11和R12相互独立地代表氢或烷基。
除此而外，还已发现式(I)新的3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物的特征在于其显著的杀螨、杀虫和除草活性，这使其适于作为农药应用。
优选式(I)化合物为以下定义的式(I)化合物及其立体异构和对映异构纯的化合物，其中：
X代表C1-C6烷基，卤素，C1-C6烷氧基或C1-C3卤代烷基，
Y代表氢，C1-C6烷基，卤素，C1-C6烷氧基或C1-C3卤代烷基，
Z代表C1-C6烷基，卤素或C1-C6烷氧基，
n代表0-3的数，或
X和Z与其连接的苯基一起形成下式的萘基：
Figure C0010194900151
其中Y定义同上，或其中：
A和B与其连接的碳原子一起形成饱和或不饱和3-8元环，该环可被C1-C6烷氧基，C1-C4烷硫基，C1-C4烷基亚磺酰基或C1-C4烷基磺酰基，羧基或CO2R2取代，或
A和B与其连接的碳原子一起代表C3-C8元环，该环中两个取代基与其连接的碳原子一起代表饱和C5-C7环，该饱和环可任选被C1-C6烷基，C1-C6烷氧基或卤素取代并且可被氧或硫间断，
G代表氢(a)或下列各式的基团：
-CO-R1，  (b)
Figure C0010194900152
-SO2-R3  (d)
E(g)
其中E代表当量金属离子或铵离子，
L和M各自代表氧或硫，
R1代表在每一情况下均可任选被卤代的C1-C20烷基，C2-C20烯基，C1-C8烷氧基C1-C8烷基，C1-C8烷硫基C1-C8烷基，C1-C8多烷氧基C1-C8烷基或C3-C8环烷基，该基团可任选被卤素或C1-C6烷基取代并且可被至少一个氧和/或硫原子间断，
可任选被卤素，硝基，C1-C6烷基，C1-C6烷氧基，C1-C6卤代烷基或C1-C6卤代烷氧基取代的苯基，
可任选被卤素，C1-C6烷基，C1-C6烷氧基，C1-C6卤代烷基或C1-C6卤代烷氧基取代的苯基C1-C6烷基，
可任选被卤素和/或C1-C6烷基取代的杂芳基，
可任选被卤素和/或C1-C6烷基取代的苯氧基C1-C6烷基，
可任选被卤素，氨基和/或C1-C6烷基取代的杂芳氧基C1-C6烷基，
R2代表C1-C20烷基，C3-C20烯基，C1-C8烷氧基C2-C8烷基或C1-C8多烷氧基C2-C8烷基，其中每一基团均可任选被卤素取代，
可任选被卤素或C1-C6烷基取代的C3-C8环烷基，
苯基或苄基，其中每一基团均可任选被卤素，硝基，C1-C6烷基，C1-C6烷氧基或C1-C6卤代烷基取代，
R3，R4和R5相互独立地代表C1-C8烷基，C1-C8烷氧基，C1-C8烷基氨基，二(C1-C8)烷基氨基，C1-C8烷硫基，C2-C5烯硫基，C2-C5炔硫基或C3-C7环烷硫基，其中每一基团可任选被卤素取代，或代表苯基，苯氧基或苯硫基，其中每一基团可任选被卤素，硝基，氰基，C1-C4烷氧基，C1-C4卤代烷氧基，C1-C4烷硫基，C1-C4卤代烷硫基，C1-C4烷基或C1-C4卤代烷基取代，
R6和R7相互独立地代表氢或代表C1-C20烷基，C1-C20烷氧基，C3-C8烯基或C1-C20烷氧基C1-C20烷基，其中每一基团均可任选被卤素取代，可任选被卤素，C1-C20卤代烷基，C1-C20烷基或C1-C20烷氧基取代的苯基，可任选被卤素，C1-C20烷基，C1-C20卤代烷基或C1-C20烷氧基取代的苄基，或一起代表可任选被氧或硫间断的C4-C6亚烷环。
特别优选的式(I)化合物为以下定义的式(I)化合物及其立体异构和对映异构纯的化合物，其中：
X代表C1-C6烷基，卤素，C1-C6烷氧基或C1-C2卤代烷基，
Y代表氢，C1-C6烷基，卤素，C1-C6烷氧基或C1-C2卤代烷基，
Z代表C1-C4烷基，卤素或C1-C4烷氧基，
n代表0-2的数，或
X和Z与其连接的苯基一起形成下式的萘基：
Figure C0010194900171
其中Y定义同上，或其中：
A和B与其连接的碳原子一起形成饱和或不饱和5-7元环，该环可被C1-C5烷氧基，C1-C3烷硫基，C1-C3烷基亚磺酰基或C1-C3烷基磺酰基，羧基或CO2R2取代，或
A和B与其连接的碳原子一起代表C4-C7元环，该环中两个取代基与其连接的碳原子一起代表饱和C5-C6环，该饱和环可任选被C1-C3烷基，C1-C3烷氧基，氟或氯取代并且可被氧或硫间断，
G代表氢(a)或下列各式的基团：
-CO-R1，  (b)
Figure C0010194900181
-SO2-R3  (d)
E  (g)
其中E代表当量金属离子或铵离子，
L和M各自代表氧或硫，
R1代表在每一情况下均可任选被卤代的C1-C16烷基，C2-C16烯基，C1-C6烷氧基C1-C6烷基，C1-C6烷硫基C1-C6烷基，C1-C6多烷氧基C1-C6烷基或C3-C7环烷基，该基团可任选被氯或C1-C4烷基取代并且可被1-2个氧和/或硫原子间断，
可任选被卤素，硝基，C1-C4烷基，C1-C4烷氧基，C1-C3卤代烷基或C1-C3卤代烷氧基取代的苯基，或
代表可任选被卤素，C1-C4烷基，C1-C4烷氧基，C1-C3卤代烷基或C1-C3卤代烷氧基取代的苯基C1-C4烷基，或
代表呋喃基，噻吩基，吡啶基，嘧啶基，噻唑基或吡唑基，其中每一基团可任选被卤素和/或C1-C6烷基取代，
可任选被卤素和/或C1-C4烷基取代的苯氧基C1-C5烷基，
吡啶氧基C1-C5烷基，嘧啶氧基C1-C5烷基或噻唑氧基C1-C5烷基，其中每一基团均可任选被卤素，氨基和/或C1-C4烷基取代，
R2代表每一情况下均可被卤代的C1-C6烷基，C3-C6烯基，C1-C6烷氧基C2-C6烷基或C1-C6多烷氧基C2-C6烷基，或
代表可任选被氟，氯或C1-C4烷基取代的C3-C7环烷基，
苯基或苄基，其中每一基团均可任选被卤素，硝基，C1-C4烷基，C1-C3烷氧基或C1-C3卤代烷基取代，
R3，R4和R5相互独立地代表C1-C6烷基，C1-C6烷氧基，C1-C6烷基氨基，二(C1-C6)烷基氨基，C1-C6烷硫基，C3-C4烯硫基，C2-C4炔硫基或C3-C6环烷硫基，其中每一基团可任选被卤素取代，或代表苯基，苯氧基或苯硫基，其中每一基团可任选被氟，氯，溴，硝基，氰基，C1-C3烷氧基，C1-C3卤代烷氧基，C1-C3烷硫基，C1-C3卤代烷硫基，C1-C3烷基或C1-C3卤代烷基取代，
R6和R7相互独立地代表氢或代表C1-C20烷基，C1-C20烷氧基，C3-C8烯基或C1-C20烷氧基C1-C20烷基，其中每一基团均可任选被卤素取代，或代表可任选被卤素，C1-C5卤代烷基，C1-C5烷基或C1-C5烷氧基取代的苯基，或代表可任选被卤素，C1-C5烷基，C1-C5卤代烷基或C1-C5烷氧基取代的苄基，或一起代表可任选被氧或硫间断的C4-C6亚烷环。
更特别优选的式(I)化合物为以下定义的式(I)化合物及其立体异构和对映异构纯的化合物，其中：
X代表甲基，乙基，丙基，异丙基，氟，氯，溴，甲氧基，乙氧基或三氟甲基，
Y代表氢，甲基，乙基，丙基，异丙基，丁基，异丁基，叔丁基，氟，氯，溴，甲氧基，乙氧基或三氟甲基，
Z代表甲基，乙基，异丙基，丁基，异丁基，叔丁基，氟，氯，溴，甲氧基或乙氧基，
n代表0或1，
A和B与其连接的碳原子一起形成饱和或不饱和5-6元环，该环可被C1-C4烷氧基，C1-C2烷硫基，C1-C2烷基亚磺酰基或C1-C2烷基磺酰基，羧基或CO2R2取代，或
A和B与其连接的碳原子一起代表C4-C6元环，该环中两个取代基与其连接的碳原子一起代表饱和C5-C6环，该饱和环可任选被甲基，乙基，甲氧基，乙氧基，氟或氯取代并且可被氧或硫间断，
G代表氢(a)或下列各式的基团：-CO-R1，  (b)
Figure C0010194900201
-SO2-R3  (d)
Figure C0010194900202
E(g)
其中E代表当量金属离子或铵离子，
L和M各自代表氧或硫，
R1代表在每一情况下均可任选被氟或氯取代的C1-C14烷基，C2-C14烯基，C1-C4烷氧基C1-C6烷基，C1-C4烷硫基C1-C6烷基，C1-C4多烷氧基C1-C4烷基或C3-C6环烷基，该基团可被氟，氯，甲基或乙基取代并且可被1-2个氧和/或硫原子间断，或
代表可任选被氟，氯，溴，甲基，乙基，丙基，异丙基，甲氧基，乙氧基，三氟甲基，三氟甲氧基或硝基取代的苯基，或
代表可任选被氟，氯，溴，甲基，乙基，丙基，异丙基，甲氧基，乙氧基，三氟甲基或三氟甲氧基取代的苯基C1-C3烷基，或
代表呋喃基，噻吩基，吡啶基，嘧啶基，噻唑基或吡唑基，其中每一基团均可任选被氟，氯，溴，甲基或乙基取代，或
代表可任选被氟，氯，甲基或乙基取代的苯氧基C1-C4烷基，或
代表吡啶氧基C1-C4烷基，嘧啶氧基C1-C4烷基或噻唑氧基C1-C4烷基，其中每一基团均可任选被氟，氯，氨基，甲基或乙基取代，
R2代表C1-C14烷基，C3-C14烯基，C1-C4烷氧基C2-C6烷基或C1-C4多烷氧基C2-C6烷基，其中每一基团均可任选被氟或氯取代，或
代表可任选被氟，氯，甲基或乙基取代的C3-C6环烷基，或代表苯基或苄基，其中每一基团均可任选被氟，氯，硝基，甲基，乙基，丙基，异丙基，甲氧基，乙氧基或三氟甲基取代，
R3，R4和R5相互独立地代表C1-C4烷基，C1-C4烷氧基，C1-C4烷基氨基，二(C1-C4)烷基氨基或C1-C4烷硫基，其中每一基团可任选被氟或氯取代，或代表苯基，苯氧基或苯硫基，其中每一基团可任选被氟，氯，溴，硝基，氰基，C1-C2烷氧基，C1-C4氟代烷氧基，C1-C2氯代烷氧基，C1-C2烷硫基，C1-C2氟代烷硫基，C1-C2氯代烷硫基或C1-C3烷基取代，
R6和R7相互独立地代表氢或代表C1-C10烷基，C1-C10烷氧基，C3-C6烯基或C1-C10烷氧基C1-C10烷基，其中每一基团均可任选被氟，氯或溴取代，或代表可任选被氟，氯，溴，C1-C2卤代烷基，C1-C2烷基或C1-C4烷氧基取代的苯基，或代表可任选被氟，氯，溴，C1-C4烷基，C1-C4卤代烷基或C1-C4烷氧基取代的苄基，或一起代表可任选被氧或硫间断的C4-C6亚烷环。
除了制备例中提到的化合物以外，还可单独列出式(Ia)的以下3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物。
表1
Figure C0010194900221
X         Y         Zn          A            B
Cl        Cl        H            -(CH2)4-CH(OCH3)-
Cl        Cl        H            -(CH2)3-CH(OCH3)-CH2-
Cl        Cl        H            -(CH2)2-CH(OCH3)-(CH2)2-
Cl        Cl        H            -(CH2)2-CH(OC2H5)-(CH2)2-
Cl        Cl        H            -(CH2)2-CH(OC3H7)-(CH2)2-
Cl        Cl        H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-
Cl        Cl        H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-
Cl        Cl        H            -(CH2)3-CH(SCH3)-CH2-
Cl        Cl        H            -(CH2)2-CH(SCH3)-(CH2)2-
Cl        Cl        H             
Figure C0010194900222
表1(续)
X          Y         Zn              A          B
Cl         Cl        H              
Figure C0010194900231
Cl         Cl        H              
Cl         Cl        H              
表1(续)
X         Y         Zn              A          B
Cl        Cl        H              
Cl        Cl        H              
Figure C0010194900242
Cl        Cl        H              
Figure C0010194900243
Cl        Cl        H              
表1(续)
X           Y           Zn             A              B
CH3        CH3        H            -(CH2)4-CH(OCH3)-
CH3        CH3        H            -(CH2)3-CH(OCH3)-CH2-
CH3        CH3        H            -(CH2)2-CH(OCH3)-(CH2)2-
CH3        CH3        H            -(CH2)2-CH(OC2H5)-(CH2)2-
CH3        CH3        H            -(CH2)2-CH(OC3H7)-(CH2)2-
CH3        CH3        H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-
CH3        CH3        H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-
CH3        CH3        H            -(CH2)3-CH(SCH3)-CH2-
CH3        CH3        H            -(CH2)2-CH(SCH3)-(CH2)2-
CH3        CH3        H             
Figure C0010194900251
表1(续)
X         Y            Zn           A           B
CH3      CH3         H         
CH3      CH3         H         
Figure C0010194900262
CH3      CH3         H         
CH3      CH3         H         
Figure C0010194900264
CH3      CH3         H         
Figure C0010194900265
CH3      CH3         H         
CH3      CH3         H         
表1(续)
X          Y         Zn            A              B
CH3      CH3      6-CH3        -(CH2)4-CH(OCH3)-
CH3      CH3      6-CH3        -(CH2)3-CH(OCH3)-CH2-
CH3      CH3      6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-
CH3      CH3      6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-
CH3      CH3      6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-
CH3      CH3      6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-
CH3      CH3      6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-
CH3      CH3      6-CH3        -(CH2)3-CH(SCH3)-CH2-
CH3      CH3      6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-
表1(续)
X           Y            Zn             A             B
CH3        CH3        6-CH3      
CH3        CH3        6-CH3      
CH3        CH3        6-CH3      
Figure C0010194900283
CH3        CH3        6-CH3      
Figure C0010194900284
CH3        CH3        6-CH3      
Figure C0010194900285
CH3        CH3        6-CH3      
Figure C0010194900286
表1(续)
X           Y              Zn            A             B
CH3        CH3          6-CH3            
Figure C0010194900291
CH3        CH3          6-CH3            
Figure C0010194900292
除了制备例中提到的化合物外，还可单独列出式(Ib)的下列3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物：
表2
表2(续)
X         Y         Zn      A               B                          R1
Cl        Cl        H        -(CH2)4-CH(OCH3)-                      CH3
Cl        Cl        H        -(CH2)3-CH(OCH3)-CH2-                 CH3
Cl        Cl        H        -(CH2)2-CH(OCH3)-(CH2)2-             CH3
Cl        Cl        H        -(CH2)2-CH(OC2H5)-(CH2)2-           CH3
Cl        Cl        H        -(CH2)2-CH(OC3H7)-(CH2)2-           CH3
Cl        Cl        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-        CH3
Cl        Cl        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-        CH3
Cl        Cl        H        -(CH2)3-CH(SCH3)-CH2-                  CH3
Cl        Cl        H        -(CH2)2-CH(SCH3)-(CH2)2-              CH3
Cl        Cl        H       
Figure C0010194900301
                         CH3
表2(续)
X         Y         Zn         A             B           R1
Cl        Cl        H          
Figure C0010194900311
      CH3
Cl        Cl        H     
Figure C0010194900312
      CH3
Cl        Cl        H     
Figure C0010194900313
        CH3
Cl        Cl        H              
Figure C0010194900314
        CH3
Cl        Cl        H                    CH3
Cl        Cl        H           
Figure C0010194900316
        CH3
Cl        Cl        H           
Figure C0010194900317
        CH3
表2(续)
X         Y         Zn        A               B                         R1
Cl        Cl        H        -(CH2)4-CH(OCH3)-                      i-C3H7
Cl        Cl        H        -(CH2)3-CH(OCH3)-CH2-                 i-C3H7
Cl        Cl        H        -(CH2)2-CH(OCH3)-(CH2)2-             i-C3H7
Cl        Cl        H        -(CH2)2-CH(OC2H5)-(CH2)2-           i-C3H7
Cl        Cl        H        -(CH2)2-CH(OC3H7)-(CH2)2-           i-C3H7
Cl        Cl        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-        i-C3H7
Cl        Cl        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-        i-C3H7
Cl        Cl        H        -(CH2)3-CH(SCH3)-CH2-                  i-C3H7
Cl        Cl        H        -(CH2)2-CH(SCH3)-(CH2)2-              i-C3H7
表2(续)
X         Y         Zn         A          B           R1
Cl        Cl        H               i-C3H7
Cl        Cl        H         
Figure C0010194900332
     i-C3H7
Cl        Cl        H          i-C3H7
Cl        Cl        H            i-C3H7
Cl        Cl        H                     i-C3H7
Cl        Cl        H           
Figure C0010194900336
      i-C3H7
表2(续)
X         Y         Zn          A          B         R1
Cl        Cl        H          
Figure C0010194900341
    i-C3H7
Cl        Cl        H               i-C3H7
表2(续)
X         Y         Zn           A               B                            R1
Cl        Cl        H            -(CH2)4-CH(OCH3)-                        t-C4H9
Cl        Cl        H            -(CH2)3-CH(OCH3)-CH2-                   t-C4H9
Cl        Cl        H            -(CH2)2-CH(OCH3)-(CH2)2-               t-C4H9
Cl        Cl        H            -(CH2)2-CH(OC2H5)-(CH2)2-             t-C4H9
Cl        Cl        H            -(CH2)2-CH(OC3H7)-(CH2)2-             t-C4H9
Cl        Cl        H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-          t-C4H9
Cl        Cl        H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-          t-C4H9
Cl        Cl        H            -(CH2)3-CH(SCH3)-CH2-                    t-C4H9
Cl        Cl        H            -(CH2)2-CH(SCH3)-(CH2)2-                t-C4H9
表2(续)
X         Y         Zn       A           B            R1
Cl        Cl        H       
Figure C0010194900361
       t-C4H9
Cl        Cl        H       
Figure C0010194900362
       t-C4H9
表2(续)
X         Y         Zn          A          B           R1
Cl        Cl        H       
Figure C0010194900371
   t-C4H9
Cl        Cl        H       
Figure C0010194900372
     t-C4H9
Cl        Cl        H                
Figure C0010194900373
     t-C4H9
表2(续)
X         Y         Zn    A           B            R1
Cl        Cl        H            t-C4H9
Cl        Cl        H     
Figure C0010194900382
      t-C4H9
Cl        Cl        H            t-C4H9
表2(续)
X         Y         Zn           A                B                             R1
Cl        Cl        H            -(CH2)4-CH(OCH3)-                     (CH3)2CH2Cl
Cl        Cl        H            -(CH2)3-CH(OCH3)-CH2-                (CH3)2CH2Cl
Cl        Cl        H            -(CH2)2-CH(OCH3)-(CH2)2-            (CH3)2CH2Cl
Cl        Cl        H            -(CH2)2-CH(OC2H5)-(CH2)2-          (CH3)2CH2Cl
Cl        Cl        H            -(CH2)2-CH(OC3H7)-(CH2)2-          (CH3)2CH2Cl
表2(续)
X        Y         Zn         A                         B                    R1
Cl       Cl        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-        -C(CH3)2CH2Cl
Cl       Cl        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-        -C(CH3)2CH2Cl
Cl       Cl        H        -(CH2)3-CH(SCH3)-CH2-                  -C(CH3)2CH2Cl
Cl       Cl        H        -(CH2)2-CH(SCH3)-(CH2)2-              -C(CH3)2CH2Cl
Cl       Cl        H       
Figure C0010194900401
                          -C(CH3)2CH2Cl
Cl       Cl        H                                  -C(CH3)2CH2Cl
表2(续)
X         Y         Zn                  A           B                 R1
Cl        Cl        H   
Figure C0010194900411
                   -C(CH3)2CH2Cl
Cl        Cl        H   
Figure C0010194900412
                    -C(CH3)2CH2Cl
Cl        Cl        H           
Figure C0010194900413
                     -C(CH3)2CH2Cl
表2(续)
X         Y         Zn          A            B              R1
Cl        Cl        H                  -C(CH3)2CH2Cl
Cl        Cl        H                  -C(CH3)2CH2Cl
表2(续)
X         Y         Zn            A                  B                    R1
Cl        Cl        H                               -C(CH3)2CH2Cl
Cl        Cl        H        -(CH2)4-CH(OCH3)-                   -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)3-CH(OCH3)-CH2-              -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)2-CH(OCH3)-(CH2)2-          -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)2-CH(OC2H5)-(CH2)2-        -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)2-CH(OC3H7)-(CH2)2-        -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-     -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-     -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)3-CH(SCH3)-CH2-               -C(CH3)2CH2CH3
Cl        Cl        H        -(CH2)2-CH(SCH3)-(CH2)2-           -C(CH3)2CH2CH3
表2(续)
X         Y         Zn                  A          B           R1
Cl        Cl        H        
Figure C0010194900441
            -C(CH3)2CH2CH3
Cl        Cl        H        
Figure C0010194900442
            -C(CH3)2CH2CH3
Cl        Cl        H    
Figure C0010194900443
            -C(CH3)2CH2CH3
Cl        Cl        H    
Figure C0010194900444
              -C(CH3)2CH2CH3
表2(续)
X         Y         Zn           A           B            R1
Cl        Cl        H                    -C(CH3)2CH2CH3
Cl        Cl        H                 -C(CH3)2CH2CH3
Cl        Cl        H    
Figure C0010194900453
            -C(CH3)2CH2CH3
Cl        Cl        H    
Figure C0010194900454
            -C(CH3)2CH2CH3
表2(续)
X            Y           Zn           A                    B                       R1
CH3        CH3        H            -(CH2)4-CH(OCH3)-                         CH3
CH3        CH3        H            -(CH2)3-CH(OCH3)-CH2-                    CH3
CH3        CH3        H            -(CH2)2-CH(OCH3)-(CH2)2-                CH3
CH3        CH3        H            -(CH2)2-CH(OC2H5)-(CH2)2-              CH3
CH3        CH3        H            -(CH2)2-CH(OC3H7)-(CH2)2-              CH3
CH3        CH3        H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-           CH3
CH3        CH3        H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-           CH3
CH3        CH3        H            -(CH2)3-CH(SCH3)-CH2-                     CH3
CH3        CH3        H            -(CH2)2-CH(SCH3)-(CH2)2-                 CH3
CH3        CH3        H                                         CH3
表2(续)
X          Y          Zn                  A              B              R1
CH3      CH3       H                               CH3
CH3      CH3       H  
Figure C0010194900472
                       CH3
CH3      CH3       H                            CH3
CH3      CH3       H             
Figure C0010194900474
                       CH3
表2(续)
X         Y            Zn              A           B              R1
CH3      CH3        H                          CH3
CH3      CH3        H   
Figure C0010194900482
                      CH3
CH3      CH3        H   
Figure C0010194900483
                      CH3
表2(续)
X           Y            Zn       A               B                          R1
CH3        CH3        H        -(CH2)4-CH(OCH3)-                      i-C3H7
CH3        CH3        H        -(CH2)3-CH(OCH3)-CH2-                 i-C3H7
CH3        CH3        H        -(CH2)2-CH(OCH3)-(CH2)2-             i-C3H7
CH3        CH3        H        -(CH2)2-CH(OC2H5)-(CH2)2-           i-C3H7
CH3        CH3        H        -(CH2)2-CH(OC3H7)-(CH2)2-           i-C3H7
CH3        CH3        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-        i-C3H7
CH3        CH3        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-        i-C3H7
CH3        CH3        H        -(CH2)3-CH(SCH3)-CH2-                  i-C3H7
CH3        CH3        H        -(CH2)2-CH(SCH3)-(CH2)2-              i-C3H7
表2(续)
X          Y           Zn                 A              B        R1
CH3      CH3        H                        i-C3H7
CH3      CH3        H       
Figure C0010194900502
                i-C3H7
CH3      CH3        H   
Figure C0010194900503
               i-C3H7
CH3      CH3        H   
Figure C0010194900504
                 i-C3H7
CH3      CH3        H           
Figure C0010194900505
                  i-C3H7
表2(续)
X         Y            Zn             A           B            R1
CH3      CH3        H                      i-C3H7
CH3      CH3        H   
Figure C0010194900512
                  i-C3H7
CH3      CH3        H                      i-C3H7
表2(续)
X            Y           Zn           A               B                      R1
CH3        CH3        H        -(CH2)4-CH(OCH3)-                      t-C4H9
CH3        CH3        H        -(CH2)3-CH(OCH3)-CH2-                 t-C4H9
CH3        CH3        H        -(CH2)2-CH(OCH3)-(CH2)2-             t-C4H9
CH3        CH3        H        -(CH2)2-CH(OC2H5)-(CH2)2-           t-C4H9
CH3        CH3        H        -(CH2)2-CH(OC3H7)-(CH2)2-           t-C4H9
CH3        CH3        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-        t-C4H9
CH3        CH3        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-        t-C4H9
CH3        CH3        H        -(CH2)3-CH(SCH3)-CH2-                  t-C4H9
CH3        CH3        H        -(CH2)2-CH(SCH3)-(CH2)2-              t-C4H9
CH3        CH3        H       
Figure C0010194900521
                          t-C4H9
CH3        CH3        H                                  t-C4H9
表2(续)
X         Y            Zn                     A           B             R1
CH3      CH3        H     
Figure C0010194900531
                   t-C4H9
CH3      CH3        H                           t-C4H9
CH3      CH3        H             
Figure C0010194900533
                      t-C4H9
CH3      CH3        H                                 t-C4H9
CH3      CH3        H                                 t-C4H9
CH3      CH3        H                                 t-C4H9
表2(续)
X            Y           Zn       A               B                              R1
CH3        CH3        H        -(CH2)4-CH(OCH3)-                      -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)3-CH(OCH3)-CH2-                 -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)2-CH(OCH3)-(CH2)2-             -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)2-CH(OC2H5)-(CH2)2-           -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)2-CH(OC3H7)-(CH2)2-           -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-        -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-        -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)3-CH(SCH3)-CH2-                  -C(CH3)2CH2Cl
CH3        CH3        H        -(CH2)2-CH(SCH3)-(CH2)2-              -C(CH3)2CH2Cl
表2(续)
X          Y           Zn                   A         B           R1
CH3      CH3        H        
Figure C0010194900551
             -C(CH3)2CH2Cl
CH3      CH3        H                      -C(CH3)2CH2Cl
CH3      CH3        H    
Figure C0010194900553
            -C(CH3)2CH2Cl
表2(续)
X          Y           Zn               A            B          R1
CH3      CH3        H  
Figure C0010194900561
              -C(CH3)2CH2Cl
CH3      CH3        H                         -C(CH3)2CH2Cl
CH3      CH3        H       
Figure C0010194900563
              -C(CH3)2CH2Cl
CH3      CH3        H       
Figure C0010194900564
              -C(CH3)2CH2Cl
表2(续)
X          Y           Zn              A            B                        R1
CH3      CH3        H       
Figure C0010194900571
                           -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)4-CH(OCH3)-                     -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)3-CH(OCH3)-CH2-                -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)2-CH(OCH3)-(CH2)2-            -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)2-CH(OC2H5)-(CH2)2-          -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)2-CH(OC3H7)-(CH2)2-          -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-       -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-       -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)3-CH(SCH3)-CH2-                 -C(CH3)2CH2CH3
CH3      CH3        H        -(CH2)2-CH(SCH3)-(CH2)2-             -C(CH3)2CH2CH3
表2(续)
X          Y           Zn                 A             B           R1
CH3      CH3        H                          -C(CH3)2CH2CH3
CH3      CH3        H                          -C(CH3)2CH2CH3
CH3      CH3        H                      -C(CH3)2CH2CH3
CH3      CH3        H                        -C(CH3)2CH2CH3
表2(续)
X          Y           Zn              A            B            R1
CH3      CH3        H         
Figure C0010194900591
                -C(CH3)2CH2CH3
CH3      CH3        H       
Figure C0010194900592
               -C(CH3)2CH2CH3
CH3      CH3        H       
Figure C0010194900593
               -C(CH3)2CH2CH3
CH3      CH3        H       
Figure C0010194900594
               -C(CH3)2CH2CH3
表2(续)
X            Y           Zn                A                  B                    R1
CH3        CH3        6-CH3        -(CH2)4-CH(OCH3)-                        CH3
CH3        CH3        6-CH3        -(CH2)3-CH(OCH3)-CH2-                   CH3
CH3        CH3        6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-               CH3
CH3        CH3        6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-             CH3
CH3        CH3        6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-             CH3
CH3        CH3        6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-          CH3
CH3        CH3        6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-          CH3
CH3        CH3        6-CH3        -(CH2)3-CH(SCH3)-CH2-                    CH3
CH3        CH3        6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-                CH3
CH3        CH3        6-CH3       
Figure C0010194900601
                            CH3
表2(续)
X          Y         Zn                    A           B          R1
CH3      CH3      6-CH3    
Figure C0010194900611
                CH3
CH3      CH3      6-CH3                 CH3
CH3      CH3      6-CH3                   CH3
CH3      CH3      6-CH3        
Figure C0010194900614
                  CH3
表2(续)
X          Y           Zn            A            B             R1
CH3      CH3        6-CH3      
Figure C0010194900621
            CH3
CH3      CH3        6-CH3      
Figure C0010194900622
            CH3
CH3      CH3        6-CH3      
Figure C0010194900623
            CH3
CH3      CH3        6-CH3       -(CH2)4-CH(OCH3)-        i-C3H7
CH3      CH3        6-CH3       -(CH2)3-CH(OCH3)-CH2-   i-C3H7
表2(续)
X            Y           Zn           A                     B                       R1
CH3        CH3        6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-              i-C3H7
CH3        CH3        6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-            i-C3H7
CH3        CH3        6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-            i-C3H7
CH3        CH3        6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-         i-C3H7
CH3        CH3        6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-         i-C3H7
CH3        CH3        6-CH3        -(CH2)3-CH(SCH3)-CH2-                   i-C3H7
CH3        CH3        6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-               i-C3H7
表2(续)
X          Y         Zn                    A              B           R1
CH3      CH3      6-CH3                        i-C3H7
CH3      CH3      6-CH3                        i-C3H7
CH3      CH3      6-CH3
Figure C0010194900643
                   i-C3H7
CH3      CH3      6-CH3
Figure C0010194900644
                     i-C3H7
CH3      CH3      6-CH3        
Figure C0010194900645
                    i-C3H7
表2(续)
X          Y         Zn                A              B             R1
CH3      CH3      6-CH3  
Figure C0010194900651
                      i-C3H7
CH3      CH3      6-CH3                         i-C3H7
CH3      CH3      6-CH3  
Figure C0010194900653
                      i-C3H7
表2(续)
X            Y           Zn           A                   B                       R1
CH3        CH3        6-CH3        -(CH2)4-CH(OCH3)-                       t-C4H9
CH3        CH3        6-CH3        -(CH2)3-CH(OCH3)-CH2-                  t-C4H9
CH3        CH3        6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-              t-C4H9
CH3        CH3        6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-            t-C4H9
CH3        CH3        6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-            t-C4H9
CH3        CH3        6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-         t-C4H9
CH3        CH3        6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-         t-C4H9
CH3        CH3        6-CH3        -(CH2)3-CH(SCH3)-CH2-                   t-C4H9
CH3        CH3        6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-               t-C4H9
CH3        CH3        6-CH3       
Figure C0010194900661
                           t-C4H9
CH3        CH3        6-CH3       
Figure C0010194900662
                           t-C4H9
表2(续)
X          Y           Zn                     A              B          R1
CH3      CH3        6-CH3  
Figure C0010194900671
                 t-C4H9
CH3      CH3        6-CH3                      t-C4H9
CH3      CH3        6-CH3                               t-C4H9
CH3      CH3        6-CH3       
Figure C0010194900674
                    t-C4H9
CH3      CH3        6-CH3       
Figure C0010194900675
                    t-C4H9
CH3      CH3        6-CH3       
Figure C0010194900676
                    t-C4H9
表2(续)
X            Y           Zn             A               B                               R1
CH3        CH3        6-CH3        -(CH2)4-CH(OCH3)-                       -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)3-CH(OCH3)-CH2-                  -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-              -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-            -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-            -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-         -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-         -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)3-CH(SCH3)-CH2-                   -C(CH3)2CH2Cl
CH3        CH3        6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-               -C(CH3)2CH2Cl
表2(续)
X          Y         Zn                  A             B           R1
CH3      CH3      6-CH3    
Figure C0010194900691
                 -C(CH3)2CH2Cl
CH3      CH3      6-CH3                      -C(CH3)2CH2Cl
CH3      CH3      6-CH3                   -C(CH3)2CH2Cl
CH3      CH3      6-CH3
Figure C0010194900694
                   -C(CH3)2CH2Cl
CH3      CH3      6-CH3       
Figure C0010194900695
                   -C(CH3)2CH2Cl
CH3      CH3      6-CH3    
Figure C0010194900696
                   -C(CH3)2CH2Cl
表2(续)
X          Y         Zn               A            B              R1
CH3      CH3      6-CH3  
Figure C0010194900701
                -C(CH3)2CH2Cl
CH3      CH3      6-CH3  
Figure C0010194900702
                -C(CH3)2CH2Cl
表2(续)
X          Y         Zn           A               B                            R1
CH3      CH3      6-CH3        -(CH2)4-CH(OCH3)-                   -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)3-CH(OCH3)-CH2-              -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-          -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-        -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-        -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-     -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-     -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)3-CH(SCH3)-CH2-               -C(CH3)2CH2CH3
CH3      CH3      6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-           -C(CH3)2CH2CH3
表2(续)
X          Y         Zn                   A                B           R1
CH3      CH3      6-CH3     
Figure C0010194900721
                     -C(CH3)2CH2CH3
CH3      CH3      6-CH3     
Figure C0010194900722
                     -C(CH3)2CH2CH3
CH3      CH3      6-CH3 
Figure C0010194900723
                     -C(CH3)2CH2CH3
表2(续)
X          Y           Zn                    A            B         R1
CH3      CH3        6-CH3                 -C(CH3)2CH2CH3
CH3      CH3        6-CH3        
Figure C0010194900732
                -C(CH3)2CH2CH3
CH3      CH3        6-CH3     
Figure C0010194900733
                -C(CH3)2CH2CH3
CH3      CH3        6-CH3     
Figure C0010194900734
                -C(CH3)2CH2CH3
CH3      CH3        6-CH3     
Figure C0010194900735
                -C(CH3)2CH2CH3
除了制备例中提到的化合物外，还可单独列出式(Ic)的下列3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物：
表3
Figure C0010194900741
X         Y         Zn        A               B                    L        M        R2
Cl        Cl        H        -(CH2)4-CH(OCH3)-                  O        O        C2H5
Cl        Cl        H        -(CH2)3-CH(OCH3)-CH2-             O        O        C2H5
Cl        Cl        H        -(CH2)2-CH(OCH3)-(CH2)2-         O        O        C2H5
Cl        Cl        H        -(CH2)2-CH(OC2H5)-(CH2)2-       O        O        C2H5
Cl        Cl        H        -(CH2)2-CH(OC3H7)-(CH2)2-       O        O        C2H5
Cl        Cl        H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-    O        O        C2H5
Cl        Cl        H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-    O        O        C2H5
Cl        Cl        H        -(CH2)3-CH(SCH3)-CH2-              O        O        C2H5
Cl        Cl        H        -(CH2)2-CH(SCH3)-(CH2)2-          O        O        C2H5
表3(续)
X       Y       Zn                 A         B         L       M       R2
Cl      Cl      H                    O       O      C2H5
Cl      Cl      H      
Figure C0010194900752
             O       O      C2H5
Cl      Cl      H 
Figure C0010194900753
             O       O      C2H5
Cl      Cl      H                 O       O      C2H5
Cl      Cl      H         
Figure C0010194900755
                O       O      C2H5
Cl      Cl      H                      O       O      C2H5
表3(续)
X       Y       Zn        A                 B                 L      M     R2
Cl      Cl      H                              O      O     C2H5
Cl      Cl      H   
Figure C0010194900762
                          O      O     C2H5
Cl      Cl      H    -(CH2)4-CH(OCH3)-                      O      O    i-C3H7
Cl      Cl      H    -(CH2)3-CH(OCH3)-CH2-                 O      O    i-C3H7
Cl      Cl      H    -(CH2)2-CH(OCH3)-(CH2)2-             O      O    i-C3H7
Cl      Cl      H    -(CH2)2-CH(OC2H5)-(CH2)2-           O      O    i-C3H7
Cl      Cl      H    -(CH2)2-CH(OC3H7)-(CH2)2-           O      O    i-C3H7
Cl      Cl      H    -(CH2)2-CH(O-i-C3H7)-(CH2)2-        O      O    i-C3H7
Cl      Cl      H    -(CH2)2-CH(O-t-C4H9)-(CH2)2-        O      O    i-C3H7
Cl      Cl      H    -(CH2)3-CH(SCH3)-CH2-                  O      O    i-C3H7
Cl      Cl      H    -(CH2)2-CH(SCH3)-(CH2)2-              O      O    i-C3H7
表3(续)
X       Y       Zn      A                         B           L      M      R2
Cl      Cl      H       
Figure C0010194900771
                    O      O      i-C3H7
Cl      Cl      H                            O      O      i-C3H7
Cl      Cl      H       
Figure C0010194900773
               O      O      i-C3H7
Cl      Cl      H                         O      O      i-C3H7
Cl      Cl      H       
Figure C0010194900775
                         O      O      i-C3H7
Cl      Cl      H       
Figure C0010194900776
                      O      O      i-C3H7
表3(续)
X     Y      Zn           A                 B                  L    M     R2
Cl    Cl     H           
Figure C0010194900781
                     O    O     i-C3H7
Cl    Cl     H           
Figure C0010194900782
                     O    O     i-C3H7
Cl    Cl     H            -(CH2)4-CH(OCH3)-                  O    S     i-C3H7
Cl    Cl     H            -(CH2)3-CH(OCH3)-CH2-             O    S     i-C3H7
Cl    Cl     H            -(CH2)2-CH(OCH3)-(CH2)2-         O    S     i-C3H7
Cl    Cl     H            -(CH2)2-CH(OC2H5)-(CH2)2-       O    S     i-C3H7
Cl    Cl     H            -(CH2)2-CH(OC3H7)-(CH2)2-       O    S     i-C3H7
Cl    Cl     H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-    O    S     i-C3H7
Cl    Cl     H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-    O    S     i-C3H7
Cl    Cl     H            -(CH2)3-CH(SCH3)-CH2-              O    S     i-C3H7
Cl    Cl     H            -(CH2)2-CH(SCH3)-(CH2)2-          O    S     i-C3H7
表3(续)
X       Y       Zn       A                      B           L      M      R2
Cl      Cl      H       
Figure C0010194900791
                 O      S      i-C3H7
Cl      Cl      H                         O      S      i-C3H7
Cl      Cl      H                    O      S      i-C3H7
Cl      Cl      H       
Figure C0010194900794
              O      S      i-C3H7
Cl      Cl      H                               O      S      i-C3H7
Cl      Cl      H       
Figure C0010194900796
                    O      S      i-C3H7
表3(续)
X     Y     Zn              A                       B               L       M         R2
Cl    Cl    H               
Figure C0010194900801
                       O       S        i-C3H7
Cl    Cl    H                                       O       S        i-C3H7
Cl    Cl    H                -(CH2)4-CH(OCH3)-                   O       O        i-C4H9
Cl    Cl    H                -(CH2)3-CH(OCH3)-CH2-              O       O        i-C4H9
Cl    Cl    H                -(CH2)2-CH(OCH3)-(CH2)2-          O       O        i-C4H9
Cl    Cl    H                -(CH2)2-CH(OC2H5)-(CH2)2-        O       O        i-C4H9
Cl    Cl    H                -(CH2)2-CH(OC3H7)-(CH2)2-        O       O        i-C4H9
Cl    Cl    H                -(CH2)2-CH(O-i-C3H7)-(CH2)2-     O       O        i-C4H9
Cl    Cl    H                -(CH2)2-CH(O-t-C4H9)-(CH2)2-     O       O        i-C4H9
Cl    Cl    H                -(CH2)3-CH(SCH3)-CH2-               O       O        i-C4H9
Cl    Cl    H                -(CH2)2-CH(SCH3)-(CH2)2-           O       O        i-C4H9
表3(续)
X       Y       Zn         A                     B              L      M       R2
Cl      Cl      H                             O      O      i-C4H9
Cl      Cl      H          
Figure C0010194900812
                  O      O      i-C4H9
Cl      Cl      H          
Figure C0010194900813
             O      O      i-C4H9
Cl      Cl      H          
Figure C0010194900814
              O      O      i-C4H9
Cl      Cl      H                                  O      O      i-C4H9
Cl      Cl      H          
Figure C0010194900816
                    O      O      i-C4H9
表3(续)
X     Y     Zn              A                     B                   L    M        R2
Cl    Cl    H               
Figure C0010194900821
                         O    O        i-C4H7
Cl    Cl    H                                         O    O        i-C4H7
Cl    Cl    H                -(CH2)4-CH(OCH3)-                      O    O        s-C4H9
Cl    Cl    H                -(CH2)3-CH(OCH3)-CH2-                 O    O        s-C4H9
Cl    Cl    H                -(CH2)2-CH(OCH3)-(CH2)2-             O    O        s-C4H9
Cl    Cl    H                -(CH2)2-CH(OC2H5)-(CH2)2-           O    O        s-C4H9
Cl    Cl    H                -(CH2)2-CH(OC3H7)-(CH2)2-           O    O        s-C4H9
Cl    Cl    H                -(CH2)2-CH(O-i-C3H7)-(CH2)2-        O    O        s-C4H9
Cl    Cl    H                -(CH2)2-CH(O-t-C4H9)-(CH2)2-        O    O        s-C4H9
Cl    Cl    H                -(CH2)3-CH(SCH3)-CH2-                  O    O        s-C4H9
Cl    Cl    H                -(CH2)2-CH(SCH3)-(CH2)2-              O    O        s-C4H9
表3(续)
X       Y       Zn          A                  B                L    M    R2
Cl      Cl      H                             O    O    s-C4H9
Cl      Cl      H                             O    O    s-C4H9
Cl      Cl      H          
Figure C0010194900833
             O    O    s-C4H9
Cl      Cl      H          
Figure C0010194900834
               O    O    s-C4H9
Cl      Cl      H          
Figure C0010194900835
                        O    O    s-C4H9
Cl      Cl      H                                O    O    s-C4H9
表3(续)
X        Y       Zn           A                 B                  L        M        R2
Cl       Cl      H           
Figure C0010194900841
                     O        O        s-C4H9
Cl       Cl      H           
Figure C0010194900842
                     O        O        s-C4H9
CH3    CH3    H            -(CH2)4-CH(OCH3)-                  O        O        C2H5
CH3    CH3    H            -(CH2)3-CH(OCH3)-CH2-             O        O        C2H5
CH3    CH3    H            -(CH2)2-CH(OCH3)-(CH2)2-         O        O        C2H5
CH3    CH3    H            -(CH2)2-CH(OC2H5)-(CH2)2-       O        O        C2H5
CH3    CH3    H            -(CH2)2-CH(OC3H7)-(CH2)2-       O        O        C2H5
CH3    CH3    H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-    O        O        C2H5
CH3    CH3    H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-    O        O        C2H5
CH3    CH3    H            -(CH2)3-CH(SCH3)-CH2-              O        O        C2H5
CH3    CH3    H            -(CH2)2-CH(SCH3)-(CH2)2-          O        O        C2H5
表3(续)
X          Y         Zn            A             B                L      M      R2
CH3      CH3      H                          O      O      C2H5
CH3      CH3      H                          O      O      C2H5
CH3      CH3      H   
Figure C0010194900853
                 O      O      C2H5
CH3      CH3      H   
Figure C0010194900854
                   O      O      C2H5
CH3      CH3      H   
Figure C0010194900855
                            O      O      C2H5
CH3      CH3      H   
Figure C0010194900856
                         O      O      C2H5
表3(续)
X        Y       Zn           A                   B                  L        M        R2
CH3    CH3    H           
Figure C0010194900861
                        O        O        C2H5
CH3    CH3    H           
Figure C0010194900862
                        O        O        C2H5
CH3    CH3    H            -(CH2)4-CH(OCH3)-                    O        O        i-C3H7
CH3    CH3    H            -(CH2)3-CH(OCH3)-CH2-               O        O        i-C3H7
CH3    CH3    H            -(CH2)2-CH(OCH3)-(CH2)2-           O        O        i-C3H7
CH3    CH3    H            -(CH2)2-CH(OC2H5)-(CH2)2-         O        O        i-C3H7
CH3    CH3    H            -(CH2)2-CH(OC3H7)-(CH2)2-         O        O        i-C3H7
CH3    CH3    H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-      O        O        i-C3H7
CH3    CH3    H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-      O        O        i-C3H7
CH3    CH3    H            -(CH2)3-CH(SCH3)-CH2-                O        O        i-C3H7
CH3    CH3    H            -(CH2)2-CH(SCH3)-(CH2)2-            O        O        i-C3H7
表3(续)
X        Y       Zn        A                    B          L    M     R2
CH3    CH3    H                        O    O    i-C3H7
CH3    CH3    H       
Figure C0010194900872
                O    O    i-C3H7
CH3    CH3    H                   O    O    i-C3H7
CH3    CH3    H                     O    O    i-C3H7
CH3    CH3    H       
Figure C0010194900875
                     O    O    i-C3H7
CH3    CH3    H       
Figure C0010194900876
                  O    O    i-C3H7
表3(续)
X        Y       Zn           A                  B                  L        M        R2
CH3    CH3    H           
Figure C0010194900881
                      O        O        i-C3H7
CH3    CH3    H           
Figure C0010194900882
                      O        O        i-C3H7
CH3    CH3    H            -(CH2)4-CH(OCH3)-                   O        S        i-C3H7
CH3    CH3    H            -(CH2)3-CH(OCH3)-CH2-              O        S        i-C3H7
CH3    CH3    H            -(CH2)2-CH(OCH3)-(CH2)2-          O        S        i-C3H7
CH3    CH3    H            -(CH2)2-CH(OC2H5)-(CH2)2-        O        S        i-C3H7
CH3    CH3    H            -(CH2)2-CH(OC3H7)-(CH2)2-        O        S        i-C3H7
CH3    CH3    H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-     O        S        i-C3H7
CH3    CH3    H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-     O        S        i-C3H7
CH3    CH3    H            -(CH2)3-CH(SCH3)-CH2-               O        S        i-C3H7
CH3    CH3    H            -(CH2)2-CH(SCH3)-(CH2)2-           O        S        i-C3H7
表3(续)
X        Y       Zn        A                  B           L    M     R2
CH3    CH3    H                       O    S    i-C3H7
CH3    CH3    H     
Figure C0010194900892
                 O    S    i-C3H7
CH3    CH3    H                  O    S    i-C3H7
CH3    CH3    H                    O    S    i-C3H7
CH3    CH3    H     
Figure C0010194900895
                      O    S    i-C3H7
CH3    CH3    H                         O    S    i-C3H7
表3(续)
X        Y       Zn           A                       B                    L        M        R2
CH3    CH3    H           
Figure C0010194900901
                              O        S        i-C3H7
CH3    CH3    H           
Figure C0010194900902
                              O        S        i-C3H7
CH3    CH3    H            -(CH2)4-CH(OCH3)-                          O        O        i-C4H9
CH3    CH3    H            -(CH2)3-CH(OCH3)-CH2-                     O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(OCH3)-(CH2)2-                 O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(OC2H5)-(CH2)2-               O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(OC3H7)-(CH2)2-               O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-            O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-            O        O        i-C4H9
CH3    CH3    H            -(CH2)3-CH(SCH3)-CH2-                      O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(SCH3)-(CH2)2-                  O        O        i-C4H9
表3(续)
X        Y       Zn      A                  B               L    M     R2
CH3    CH3    H      
Figure C0010194900911
                  O    O    i-C4H9
CH3    CH3    H                         O    O    i-C4H9
CH3    CH3    H                    O    O    i-C4H9
CH3    CH3    H      
Figure C0010194900914
               O    O    i-C4H9
CH3    CH3    H                               O    O    i-C4H9
CH3    CH3    H      
Figure C0010194900916
                     O    O    i-C4H9
表3(续)
X        Y       Zn               A                  B                   L        M         R2
CH3    CH3    H                                        O        O        i-C4H9
CH3    CH3    H               
Figure C0010194900922
                        O        O        i-C4H9
CH3    CH3    H                -(CH2)4-CH(OCH3)-                    O        O        s-C4H9
CH3    CH3    H                -(CH2)3-CH(OCH3)-CH2-               O        O        s-C4H9
CH3    CH3    H                -(CH2)2-CH(OCH3)-(CH2)2-           O        O        s-C4H9
CH3    CH3    H                -(CH2)2-CH(OC2H5)-(CH2)2-         O        O        s-C4H9
CH3    CH3    H                -(CH2)2-CH(OC3H7)-(CH2)2-         O        O        s-C4H9
CH3    CH3    H                -(CH2)2-CH(O-i-C3H7)-(CH2)2-      O        O        s-C4H9
CH3    CH3    H                -(CH2)2-CH(O-t-C4H9)-(CH2)2-      O        O        s-C4H9
CH3    CH3    H                -(CH2)3-CH(SCH3)-CH2-                O        O        s-C4H9
CH3    CH3    H                -(CH2)2-CH(SCH3)-(CH2)2-            O        O        s-C4H9
表3(续)
X        Y       Zn           A                 B                   L        M        R2
CH3    CH3    H           
Figure C0010194900931
                      O        S        i-C3H7
CH3    CH3    H           
Figure C0010194900932
                      O        S        i-C3H7
CH3    CH3    H            -(CH2)4-CH(OCH3)-                   O        O        i-C4H9
CH3    CH3    H            -(CH2)3-CH(OCH3)-CH2-              O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(OCH3)-(CH2)2-          O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(OC2H5)-(CH2)2-        O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(OC3H7)-(CH2)2-        O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-     O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-     O        O        i-C4H9
CH3    CH3    H            -(CH2)3-CH(SCH3)-CH2-               O        O        i-C4H9
CH3    CH3    H            -(CH2)2-CH(SCH3)-(CH2)2-           O        O        i-C4H9
表3(续)
X        Y       Zn       A                     B             L    M    R2
CH3    CH3    H                          O    O    i-C4H9
CH3    CH3    H       
Figure C0010194900942
                  O    O    i-C4H9
CH3    CH3    H                     O    O    i-C4H9
CH3    CH3    H       
Figure C0010194900944
               O    O    i-C4H9
CH3    CH3    H       
Figure C0010194900945
                        O    O    i-C4H9
CH3    CH3    H                             O    O    i-C4H9
表3(续)
X        Y       Zn           A                    B                   L        M        R2
CH3    CH3    H           
Figure C0010194900951
                         O        O        i-C4H9
CH3    CH3    H                                     O        O        i-C4H9
CH3    CH3    H            -(CH2)4-CH(OCH3)-                      O        O        s-C4H9
CH3    CH3    H            -(CH2)3-CH(OCH3)-CH2-                 O        O        s-C4H9
CH3    CH3    H            -(CH2)2-CH(OCH3)-(CH2)2-             O        O        s-C4H9
CH3    CH3    H            -(CH2)2-CH(OC2H5)-(CH2)2-           O        O        s-C4H9
CH3    CH3    H            -(CH2)2-CH(OC3H7)-(CH2)2-           O        O        s-C4H9
CH3    CH3    H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-        O        O        s-C4H9
CH3    CH3    H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-        O        O        s-C4H9
CH3    CH3    H            -(CH2)3-CH(SCH3)-CH2-                  O        O        s-C4H9
CH3    CH3    H            -(CH2)2-CH(SCH3)-(CH2)2-              O        O        s-C4H9
表3(续)
X        Y       Zn        A                       B              L    M     R2
CH3    CH3    H                               O    O    s-C4H9
CH3    CH3    H                               O    O    s-C4H9
CH3    CH3    H                          O    O    s-C4H9
CH3    CH3    H        
Figure C0010194900964
                   O    O    s-C4H9
CH3    CH3    H                                     O    O    s-C4H9
CH3    CH3    H        
Figure C0010194900966
                         O    O    s-C4H9
表3(续)
X        Y       Zn               A                   B                      L        M        R2
CH3    CH3    H                 
Figure C0010194900971
                         O        O        s-C4H9
CH3    CH3    H                 
Figure C0010194900972
                         O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)4-CH(OCH3)-                      O        O        C2H5
CH3    CH3    6-CH3            -(CH2)3-CH(OCH3)-CH2-                 O        O        C2H5
CH3    CH3    6-CH3            -(CH2)2-CH(OCH3)-(CH2)2-             O        O        C2H5
CH3    CH3    6-CH3            -(CH2)2-CH(OC2H5)-(CH2)2-           O        O        C2H5
CH3    CH3    6-CH3            -(CH2)2-CH(OC3H7)-(CH2)2-           O        O        C2H5
CH3    CH3    6-CH3            -(CH2)2-CH(O-i-C3H7)-(CH2)2-        O        O        C2H5
CH3    CH3    6-CH3            -(CH2)2-CH(O-t-C4H9)-(CH2)2-        O        O        C2H5
CH3    CH3    6-CH3            -(CH2)3-CH(SCH3)-CH2-                  O        O        C2H5
CH3    CH3    6-CH3            -(CH2)2-CH(SCH3)-(CH2)2-              O        O        C2H5
表3(续)
X        Y       Zn            A                    B        L     M     R2
CH3    CH3    6-CH3                     O    O    C2H5
CH3    CH3    6-CH3     
Figure C0010194900982
               O    O    C2H5
CH3    CH3    6-CH3     
Figure C0010194900983
          O    O    C2H5
CH3    CH3    6-CH3                  O    O    C2H5
CH3    CH3    6-CH3     
Figure C0010194900985
                     O    O    C2H5
CH3    CH3    6-CH3     
Figure C0010194900986
                 O    O    C2H5
表3(续)
X        Y       Zn           A                    B                          L        M      R2
CH3    CH3    6-CH3       
Figure C0010194900991
                               O        O      C2H5
CH3    CH3    6-CH3                                       O        O      C2H5
CH3    CH3    6-CH3        -(CH2)4-CH(OCH3)-                           O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)3-CH(OCH3)-CH2-                      O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-                  O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-                O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-                O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-             O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-             O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)3-CH(SCH3)-CH2-                       O        O      i-C3H7
CH3    CH3    6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-                   O        O      i-C3H7
表3(续)
X        Y       Zn         A                  B         L    M     R2
CH3    CH3    6-CH3  
Figure C0010194901001
             O    O    i-C3H7
CH3    CH3    6-CH3  
Figure C0010194901002
             O    O    i-C3H7
CH3    CH3    6-CH3  
Figure C0010194901003
        O    O    i-C3H7
CH3    CH3    6-CH3  
Figure C0010194901004
          O    O    i-C3H7
CH3    CH3    6-CH3                      O    O    i-C3H7
CH3    CH3    6-CH3  
Figure C0010194901006
                O    O    i-C3H7
表3(续)
X        Y       Zn               A                   B                   L        M        R2
CH3    CH3    6-CH3           
Figure C0010194901011
                       O        O        i-C3H7
CH3    CH3    6-CH3           
Figure C0010194901012
                       O        O        i-C3H7
CH3    CH3    6-CH3            -(CH2)4-CH(OCH3)-                   O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)3-CH(OCH3)-CH2-              O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)2-CH(OCH3)-(CH2)2-          O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)2-CH(OC2H5)-(CH2)2-        O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)2-CH(OC3H7)-(CH2)2-        O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)2-CH(O-i-C3H7)-(CH2)2-     O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)2-CH(O-t-C4H9)-(CH2)2-     O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)3-CH(SCH3)-CH2-               O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)2-CH(SCH3)-(CH2)2-           O        S        i-C3H7
表3(续)
X        Y       Zn            A                  B             L    M     R2
CH3    CH3    6-CH3     
Figure C0010194901021
                 O    S    i-C3H7
CH3    CH3    6-CH3     
Figure C0010194901022
                 O    S    i-C3H7
CH3    CH3    6-CH3     
Figure C0010194901023
            O    S    i-C3H7
CH3    CH3    6-CH3     
Figure C0010194901024
              O    S    i-C3H7
CH3    CH3    6-CH3     
Figure C0010194901025
                      O    S    i-C3H7
CH3    CH3    6-CH3                         O    S    i-C3H7
表3(续)
X        Y       Zn               A                   B                  L       M         R2
CH3    CH3    6-CH3                                  O        S        i-C3H7
CH3    CH3    6-CH3           
Figure C0010194901032
                      O        S        i-C3H7
CH3    CH3    6-CH3            -(CH2)4-CH(OCH3)-                   O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)3-CH(OCH3)-CH2-              O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(OCH3)-(CH2)2-          O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(OC2H5)-(CH2)2-        O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(OC3H7)-(CH2)2-        O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(O-i-C3H7)-(CH2)2-     O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(O-t-C4H9)-(CH2)2-     O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)3-CH(SCH3)-CH2-               O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(SCH3)-(CH2)2-           O        O        i-C4H9
表3(续)
X        Y       Zn         A                       B             L    M     R2
CH3    CH3    6-CH3     
Figure C0010194901041
                   O    O    i-C4H9
CH3    CH3    6-CH3     
Figure C0010194901042
                   O    O    i-C4H9
CH3    CH3    6-CH3     
Figure C0010194901043
              O    O    i-C4H9
CH3    CH3    6-CH3     
Figure C0010194901044
                O    O    i-C4H9
CH3    CH3    6-CH3     
Figure C0010194901045
                         O    O    i-C4H9
CH3    CH3    6-CH3     
Figure C0010194901046
                O    O    i-C4H9
表3(续)
X        Y       Zn               A                   B                   L        M        R2
CH3    CH3    6-CH3           
Figure C0010194901051
                       O        O        i-C4H9
CH3    CH3    6-CH3           
Figure C0010194901052
                       O        O        i-C4H9
CH3    CH3    6-CH3            -(CH2)4-CH(OCH3)-                   O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)3-CH(OCH3)-CH2-              O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(OCH3)-(CH2)2-          O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(OC2H5)-(CH2)2-        O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(OC3H7)-(CH2)2-        O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(O-i-C3H7)-(CH2)2-     O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(O-t-C4H9)-(CH2)2-     O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)3-CH(SCH3)-CH2-               O        O        s-C4H9
CH3    CH3    6-CH3            -(CH2)2-CH(SCH3)-(CH2)2-           O        O        s-C4H9
表3(续)
X        Y       Zn         A                  B            L    M     R2
CH3    CH3    6-CH3                   O    O    s-C4H9
CH3    CH3    6-CH3   
Figure C0010194901062
               O    O    s-C4H9
CH3    CH3    6-CH3   
Figure C0010194901063
          O    O    s-C4H9
CH3    CH3    6-CH3                O    O    s-C4H9
CH3    CH3    6-CH3   
Figure C0010194901065
                     O    O    s-C4H9
CH3    CH3    6-CH3                      O    O    s-C4H9
表3(续)
X        Y       Zn            A              B         L    M     R2
CH3    CH3    6-CH3                 O    O    s-C4H9
CH3    CH3    6-CH3     
Figure C0010194901072
           O    O    s-C4H9
除了制备例中提到的化合物外，还可单独列出式(Ig)的下列3-芳基-4-羟基-Δ3-二氢呋喃酮衍生物：
Figure C0010194901081
表4
X     Y     Zn       A               B                            E
Cl    Cl    H        -(CH2)4-CH(OCH3)-                         Na
Cl    Cl    H        -(CH2)3-CH(OCH3)-CH2-                    Na
Cl    Cl    H        -(CH2)2-CH(OCH3)-(CH2)2-                Na
Cl    Cl    H        -(CH2)2-CH(OC2H5)-(CH2)2-              Na
Cl    Cl    H        -(CH2)2-CH(OC3H7)-(CH2)2-              Na
Cl    Cl    H        -(CH2)2-CH(O-i-C3H7)-(CH2)2-           Na
Cl    Cl    H        -(CH2)2-CH(O-t-C4H9)-(CH2)2-           Na
Cl    Cl    H        -(CH2)3-CH(SCH3)-CH2-                     Na
Cl    Cl    H        -(CH2)2-CH(SCH3)-(CH2)2-                 Na
Cl    Cl    H          
Figure C0010194901082
                           Na
表4(续)
X     Y     Zn                A                   B          E
Cl    Cl    H                
Figure C0010194901091
             Na
Cl    Cl    H                         Na
Cl    Cl    H             
Figure C0010194901093
             Na
表4(续)
X     Y     Zn               A          B              E
Cl    Cl    H                      
Figure C0010194901101
       Na
Cl    Cl    H                   
Figure C0010194901102
       Na
Cl    Cl    H                           Na
Cl    Cl    H                   
Figure C0010194901104
       Na
表4(续)
X         Y     Zn           A               B                    E
Cl        Cl    H            -(CH2)4-CH(OCH3)-               -NH3-i-C3H7
Cl        Cl    H            -(CH2)3-CH(OCH3)-CH2-          -NH3-i-C3H7
Cl        Cl    H            -(CH2)2-CH(OCH3)-(CH2)2-      -NH3-i-C3H7
表4(续)
X         Y         Zn           A                       B                      E
Cl        Cl        H            -(CH2)2-CH(OC2H5)-(CH2)2-            -NH3-i-C3H7
Cl        Cl        H            -(CH2)2-CH(OC3H7)-(CH2)2-            -NH3-i-C3H7
Cl        Cl        H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-         -NH3-i-C3H7
Cl        Cl        H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-         -NH3-i-C3H7
Cl        Cl        H            -(CH2)3-CH(SCH3)-CH2-                   -NH3-i-C3H7
Cl        Cl        H            -(CH2)2-CH(SCH3)-(CH2)2-               -NH3-i-C3H7
表4(续)
X     Y     Zn               A                   B               E
Cl    Cl    H              
Figure C0010194901131
                   -NH3-i-C3H7
Cl    Cl    H              
Figure C0010194901132
                   -NH3-i-C3H7
Cl    Cl    H                             -NH3-i-C3H7
Cl    Cl    H              
Figure C0010194901134
                -NH3-i-C3H7
Cl    Cl    H                                       -NH3-i-C3H7
Cl    Cl    H                                    -NH3-i-C3H7
表4(续)
X     Y       Zn        A           B           E
Cl    Cl      H                   -NH3-i-C3H7
Cl    Cl      H                   -NH3-i-C3H7
表4(续)
X            Y           Zn            A              B                       E
CH3        CH3        H            -(CH2)4-CH(OCH3)-                     Na
CH3        CH3        H            -(CH2)3-CH(OCH3)-CH2-                Na
CH3        CH3        H            -(CH2)2-CH(OCH3)-(CH2)2-            Na
CH3        CH3        H            -(CH2)2-CH(OC2H5)-(CH2)2-          Na
CH3        CH3        H            -(CH2)2-CH(OC3H7)-(CH2)2-          Na
CH3        CH3        H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-       Na
CH3        CH3        H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-       Na
CH3        CH3        H            -(CH2)3-CH(SCH3)-CH2-                 Na
CH3        CH3        H            -(CH2)2-CH(SCH3)-(CH2)2-             Na
表4(续)
X        Y       Zn         A             B              E
CH3    CH3    H          
Figure C0010194901161
          Na
CH3    CH3    H                     Na
CH3    CH3    H                Na
表4(续)
X        Y         Zn              A              B           E
CH3    CH3      H                     Na
CH3    CH3      H                     
Figure C0010194901172
        Na
CH3    CH3      H                           Na
CH3    CH3      H                           Na
CH3    CH3      H                  
Figure C0010194901175
        Na
表4(续)
X          Y           Zn           A               B                       E
CH3      CH3        H            -(CH2)4-CH(OCH3)-                   -NH3-i-C3H7
CH3      CH3        H            -(CH2)3-CH(OCH3)-CH2-              -NH3-i-C3H7
CH3      CH3        H            -(CH2)2-CH(OCH3)-(CH2)2-          -NH3-i-C3H7
CH3      CH3        H            -(CH2)2-CH(OC2H5)-(CH2)2-        -NH3-i-C3H7
CH3      CH3        H            -(CH2)2-CH(OC3H7)-(CH2)2-        -NH3-i-C3H7
CH3      CH3        H            -(CH2)2-CH(O-i-C3H7)-(CH2)2-     -NH3-i-C3H7
CH3      CH3        H            -(CH2)2-CH(O-t-C4H9)-(CH2)2-     -NH3-i-C3H7
CH3      CH3        H            -(CH2)3-CH(SCH3)-CH2-               -NH3-i-C3H7
CH3      CH3        H            -(CH2)2-CH(SCH3)-(CH2)2-           -NH3-i-C3H7
表4(续)
X        Y         Zn        A                B               E
CH3    CH3      H        
Figure C0010194901191
                -NH3-i-C3H7
CH3    CH3      H        
Figure C0010194901192
                -NH3-i-C3H7
CH3    CH3      H                    -NH3-i-C3H7
CH3    CH3      H                      -NH3-i-C3H7
表4(续)
X        Y         Zn     A             B               E
CH3    CH3      H                         -NH3-i-C3H7
CH3    CH3      H                      -NH3-i-C3H7
CH3    CH3      H                      -NH3-i-C3H7
CH3    CH3      H      
Figure C0010194901204
               -NH3-i-C3H7
表4(续)
X        Y           Zn           A               B                          E
CH3    CH3        6-CH3        -(CH2)4-CH(OCH3)-                       Na
CH3    CH3        6-CH3        -(CH2)3-CH(OCH3)-CH2-                  Na
CH3    CH3        6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-              Na
CH3    CH3        6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-            Na
CH3    CH3        6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-            Na
CH3    CH3        6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-         Na
CH3    CH3        6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-         Na
CH3    CH3        6-CH3        -(CH2)3-CH(SCH3)-CH2-                   Na
CH3    CH3        6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-               Na
表4(续)
X          Y         Zn             A              B              E
CH3      CH3      6-CH3                     Na
CH3      CH3      6-CH3            
Figure C0010194901222
        Na
CH3      CH3      6-CH3                Na
CH3      CH3      6-CH3        
Figure C0010194901224
         Na
CH3      CH3      6-CH3                
Figure C0010194901225
          Na
表4(续)
X          Y         Zn     A                B             E
CH3      CH3      6-CH3                Na
CH3      CH3      6-CH3     
Figure C0010194901232
          Na
CH3      CH3      6-CH3                Na
表4(续)
X         Y         Zn           A               B                             E
CH3     CH3      6-CH3        -(CH2)4-CH(OCH3)-                       -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)3-CH(OCH3)-CH2-                  -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)2-CH(OCH3)-(CH2)2-              -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)2-CH(OC2H5)-(CH2)2-            -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)2-CH(OC3H7)-(CH2)2-            -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)2-CH(O-i-C3H7)-(CH2)2-         -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)2-CH(O-t-C4H9)-(CH2)2-         -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)3-CH(SCH3)-CH2-                   -NH3-i-C3H7
CH3     CH3      6-CH3        -(CH2)2-CH(SCH3)-(CH2)2-               -NH3-i-C3H7
表4(续)
X          Y         Zn             A               B            E
CH3      CH3      6-CH3                    -NH3-i-C3H7
CH3      CH3      6-CH3    
Figure C0010194901252
               -NH3-i-C3H7
表4(续)
X          Y         Zn              A                 B          E
CH3      CH3      6-CH3                  -NH3-i-C3H7
CH3      CH3      6-CH3      
Figure C0010194901262
             -NH3-i-C3H7
CH3      CH3      6-CH3                            -NH3-i-C3H7
表4(续)
X          Y         Zn           A           B           E
CH3      CH3      6-CH3      
Figure C0010194901271
         -NH3-i-C3H7
CH3      CH3      6-CH3                -NH3-i-C3H7
CH3      CH3      6-CH3                -NH3-i-C3H7
如果按照方法(A)使用1-(2，6-二氯苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯，则本发明的反应过程可用下式表示：
Figure C0010194901274
如果按照方法(B)(变式α)使用3-(2，4，6-三甲基苯基)-4-羟基-5，5-(2-乙氧基)五亚甲基-Δ3-二氢呋喃-2-酮和新戊酰氯作起始物，则本发明的反应过程可用下式表示：
如果按照方法(B)(变式β)使用3-(2，4，6-三甲基苯基)-4-羟基-5，5-(2-甲氧基)四亚甲基-Δ3-二氢呋喃-2-酮和乙酐作起始化合物，则本发明的反应过程可用下式表示：
如果按照方法(C)使用3-(3，4-二氯苯基)-4-羟基-5，5-(3-丙氧基)五亚甲基-Δ3-二氢呋喃-2-酮和氯甲酸乙氧乙基酯作为起始化合物，则本发明方法的过程可用下式表示：
如果按照方法(Dα)使用3-(2，4，6-三甲基苯基)-3-羟基-5，5-(3-叔丁氧基)五亚甲基-Δ3-二氢呋喃-2-酮和单硫代氯甲酸甲酯作起始物，则反应过程可如下表示：
如果按照方法(E)使用3-(2，4，6-三甲基苯基-4-羟基-5，5-(1，2-四亚甲基)三亚甲基-Δ3-二氢呋喃-2-酮和甲磺酰氯作起始物，则反应过程可用下式表示：
Figure C0010194901301
如果按照方法(F)使用3-(2，4，6-三甲基苯基-4-羟基-5，5-(1，4-氧)五亚甲基-Δ3-二氢呋喃-2-酮和甲烷氯硫代膦酸2，2，2-三氟乙基酯作起始物，则反应过程可用下式表示：
Figure C0010194901302
如果按照方法(Gα)使用3-(2，4，6-三甲基苯基)-4-羟基-5，5-(2，3-四亚甲基)四亚甲基-Δ3-二氢呋喃-2-酮和异氰酸乙酯作起始物，则反应过程可用下式表示：
Figure C0010194901303
Figure C0010194901311
如果按照方法(Gβ)使用3-(2，4，6-三甲基苯基)-4-羟基-5，5-(2-甲基巯基)五亚甲基-Δ3-二氢呋喃-2-酮和二甲基氨基甲酰氯作起始物，则反应过程可用下式表示：
如果按照方法(H)使用3-(2，4，6-三甲基苯基)-4-羟基-5，5-(2-甲氧基)五亚甲基-Δ3-二氢呋喃-2-酮和NaOH作反应物，则本发明方法的过程可用下式表示：
Figure C0010194901313
Figure C0010194901321
需要在上述方法(A)中作为起始物的式(II)化合物是新化合物，但可以用原理上已知的方法加以简单制备。
其中A、B、X、Y、Z、n和R8具有上述含义。
例如，式(II)的O-酰基-α-羟基羧酸酯用如下方法制得：
a)将式(XIII)的2-羟基羧酸(酯)用式(XIV)的苯乙酰卤酰化(Chem.Reviews 52：237-416，1953)，并任选酯化；
Figure C0010194901323
其中R12代表氢(XIIIa)或烷基(XIIIb)，A和B具有上述含义；
Figure C0010194901324
其中X、Y、Z和n具有上述含义，Hal代表氯或溴；
或者使式(IIa)的羟基羧酸酯化(Chem.Ind.(London)1568，1968)：
Figure C0010194901331
其中A、B、X、Y、Z和n具有上述含义。
式(IIa)化合物可以由(例如)式(XIII)的苯乙酰卤和式(XIIIa)的羟基羧酸来制取(Chem.Reviews 52：237-416，1953)。
可以列举出下列式(II)化合物：
1-(2，4-二氯苯基乙酰氧基)-2-甲氧基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-2-甲氧基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-2-甲氧基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-2-甲氧基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-2-甲氧基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-2-甲氧基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-2-甲氧基环己烷甲酸乙酯
1-(2，4-二氯苯基乙酰氧基)-3-甲氧基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-3-甲氧基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-3-甲氧基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-3-甲氧基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-3-甲氧基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-3-甲氧基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-3-甲氧基环己烷甲酸乙酯
1-(2，4-二氯苯基乙酰氧基)-4-甲氧基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-4-甲氧基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-4-甲氧基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-4-甲氧基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-4-甲氧基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-4-甲氧基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-4-甲氧基环己烷甲酸乙酯
1-(2，4-二氯苯基乙酰氧基)-4-乙氧基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-4-乙氧基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-4-乙氧基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-4-乙氧基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-4-乙氧基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-4-乙氧基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-4-乙氧基环己烷甲酸乙酯
1-(2，4-二氯苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-4-异丙氧基环己烷甲酸乙酯
1-(2，4-二氯苯基乙酰氧基)-4-叔丁氧基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-4-叔丁氧基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-4-叔丁氧基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-4-叔丁氧基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-4-叔丁氧基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-4-叔丁氧基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-4-叔丁氧基环己烷甲酸乙酯
1-(2，4-二氯苯基乙酰氧基)-3，4-三亚甲基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-3，4-三亚甲基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-3，4-三亚甲基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-3，4-三亚甲基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-3，4-三亚甲基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-3，4-三亚甲基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-3，4-三亚甲基环己烷甲酸乙酯
1-(2，4-二氯苯基乙酰氧基)-2，5-亚甲基环己烷甲酸乙酯
1-(2，6-二氯苯基乙酰氧基)-2，5-亚甲基环己烷甲酸乙酯
1-(2-氯-6-氟苯基乙酰氧基)-2，5-亚甲基环己烷甲酸乙酯
1-(2，4-二甲基苯基乙酰氧基)-2，5-亚甲基环己烷甲酸乙酯
1-(2，6-二甲基苯基乙酰氧基)-2，5-亚甲基环己烷甲酸乙酯
1-(2，4，6-三甲基苯基乙酰氧基)-2，5-亚甲基环己烷甲酸乙酯
1-(2，6-二氯-4-三氟甲基苯基乙酰氧基)-2，5-亚甲基环己烷甲酸乙酯
方法(A)的特征是：在碱存在下，使A、B、X、Y、Z、n和R8具有上述含义的式(II)化合物进行分子内缩合反应。
可用于本发明方法(A)的稀释剂都是惰性有机溶剂。优选使用下列溶剂：烃类，如甲苯和二甲苯；醚类，如二丁醚、四氢呋喃、二噁烷、乙二醇二甲醚和二甘醇二甲醚；极性溶剂，如二甲亚砜、环丁砜、二甲基甲酰胺和N-甲基吡咯烷酮。还可以使用醇类，如甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇或叔丁醇。
进行本发明的方法(A)时可以使用的碱(脱质子剂)都是常规的质子受体。优选使用下列碱：碱金属氧化物、碱金属氢氧化物、碱金属碳酸盐、碱土金属氧化物、碱土金属氢氧化物和碱土金属碳酸盐，如氢氧化钠、氢氧化钾、氧化镁、氧化钙、碳酸钠、碳酸钾和碳酸钙，所有这些碱都可以在相转移催化剂存在下使用。相转移催化剂的例子有：氯化三乙基苄铵、溴化四丁铵、Adogen 464(氯化甲基三烷基(C8-C10)铵)或TDA 1(三(甲氧基乙氧基乙基)胺)。还可以使用碱金属，如钠或钾。可使用的其他物质有：碱金属氨化物、碱金属氢化物、碱土金属氨化物和碱土金属氢化物，如氨化钠、氢化钠和氢化钙；以及碱金属醇盐，如甲醇钠、乙醇钠和叔丁醇钾。
进行本发明的方法(A)时，反应温度可在很大范围内变化。一般来说，该方法在0℃至250℃之间，优选50℃至150℃之间的温度下进行。
本发明的方法(A)一般在常压下进行。
进行本发明的方法(A)时，通常采用约等摩尔量的式(II)反应物和脱质子碱。但其中的一个成分或另一成分可以过量较多(至多3摩尔)。
方法(Bα)的特征是：使式(Ia)的化合物与式(III)的羰基卤反应。
如果使用酰卤，则本发明的方法(Bα)中可使用的稀释剂都是对这些化合物呈惰性的溶剂。优选使用下列溶剂：烃类，如汽油、苯、甲苯、二甲苯和1，2，3，4-四氢化萘；卤代烃类，如二氯甲烷、氯仿、四氯化碳、氯苯和邻二氯苯；酮类，如丙酮和甲基异丙基酮；醚类，如乙醚、四氢呋喃和二噁烷；羧酸酯类，如乙酸乙酯；强极性溶剂，如二甲亚砜和环丁砜。如果酰卤对水解足够稳定，则反应也可在水存在下进行。
如果使用相应的羰基卤，则本发明方法(Bα)反应中的合适酸结合剂都是常规的酸受体。优选使用下列酸结合剂。叔胺，如三乙胺、吡啶、二氮杂双环辛烷(DABCO)、二氮杂双环十一烷(DBU)、二氮杂双环壬烯(DBN)、Hünig碱和N，N-二甲基苯胺；碱土金属氧化物，如氧化镁和氧化钙；碱金属碳酸盐和碱土金属碳酸盐，如碳酸钠、碳酸钾和碳酸钙。
进行本发明的方法(Bα)并使用羰基卤时，反应温度也可以在很大范围内变化。一般来说，该方法在-20℃至+150℃之间，优选0℃至100℃之间的温度下进行。
进行本发明的方法(Bα)时，一般使用约等摩尔量的式(Ia)起始物质和式(III)羰基卤。但也可采用过量较多的羰基卤(至多5摩尔)。用常规方法进行后处理。
方法(Bβ)的特征是：使式(Ia)的化合物与式(IV)的酸酐反应。
如果在本发明的方法(Bβ)中使用酸酐作为式(IV)反应物，则可以使用的合适稀释剂优选那些在使用酰卤时也是优选的适宜稀释剂。所用的过量酸酐也可以同时起到稀释剂的作用。
进行本发明的方法(Bβ)并使用酸酐时，反应温度可以在很大范围内变化。一般来说，该方法在-20℃至+150℃之间，优选0℃至100℃之间的温度下进行。
进行本发明的方法(Bβ)时，一般使用约等当量的式(Ia)起始物质和式(IV)酸酐。但也可以使用过量较多的酸酐(至多5摩尔)。用常规方法进行后处理。
一般来说，按照某种程序，通过蒸馏或者用有机溶剂或水洗涤，除去稀释剂和过量的酸酐及所形成的羧酸。
方法(C)的特征是：使式(Ia)的化合物与式(V)的氯甲酸酯或氯甲酸硫酯反应。
如果使用相应的氯甲酸酯或氯甲酸硫酯，则本发明方法(C)反应中的适宜酸受体都是常规酸受体。优选使用下列酸受体：叔胺，如三乙胺、吡啶、DABCO、DBC、DBA、Hünig碱和N，N-二甲基苯胺；碱土金属氧化物，如氧化镁和氧化钙；碱金属碳酸盐和碱土金属碳酸盐，如碳酸钠、碳酸钾和碳酸钙。
使用氯甲酸酯或氯甲酸硫酯时，可用于本发明方法(C)的稀释剂都是对这些化合物呈惰性的溶剂。优选使用下列溶剂：烃类，如汽油、苯、甲苯、二甲苯和1，2，3，4-四氢化萘；卤代烃类，如二氯甲烷、氯仿、四氯化碳、氯苯和邻二氯苯；酮类，如丙酮和甲基异丙基酮；醚类，如乙醚、四氢呋喃和二噁烷；羧酸酯类，如乙酸乙酯；强极性溶剂，如二甲亚砜和环丁砜。
进行本发明的方法(C)时，如果使用氯甲酸酯或氯甲酸硫酯作为式(V)的羧酸衍生物，则反应温度可在很大范围内变化。如果该方法在稀释剂和酸结合剂存在下进行，则反应温度一般为-20℃至+100℃之间，优选0℃至50℃之间。
本发明的方法(C)一般在常压下进行。
进行本发明的方法(C)时，一般使用约等当量的式(Ia)起始物质和具体的氯甲酸酯或氯甲酸硫酯。但其中一个成分或另一个成分也可以过量较多(至多2摩尔)。用常规方法进行后处理。一般来说，按照某种程序除去沉淀出的盐，并通过脱除溶剂浓缩留下的反应混合物。
在制备方法D中，每摩尔式(Ia)起始化合物使用约1摩尔式(VI)单硫代氯甲酸酯或二硫代氯甲酸酯，反应在0至120℃，优选20-60℃下进行。
可加入的适宜稀释剂都是惰性的极性有机溶剂，如醚类、酰胺类、醇类、砜类或亚砜类。
优选使用二甲亚砜、四氢呋喃、二甲基甲酰胺和甲硫醚。
在一个优选的实施方案中，如果通过加入强脱质子剂(如氢化钠或叔丁醇钾)来制备化合物Ia的烯醇盐，则不需要再另加酸结合剂。
如果使用酸结合剂，则适宜的物质是常规的无机或有机碱，例如氢氧化钠、碳酸钠、碳酸钾、吡啶和三乙胺。
该反应可在常压或高压下进行，优选在常压下进行。用常规方法进行后处理。
在制备方法(E)中，每摩尔式(Ia)起始化合物用约1摩尔磺酰氯(VII)进行反应，反应在0至150℃，优选20至70℃下进行。
可以加入的适宜稀释剂都是惰性的极性有机溶剂，例如醚类、酰胺类、腈类、醇类、砜类和亚砜类。
优选使用二甲亚砜、四氢呋喃、二甲基甲酰胺和甲硫醚。
在一个优选的实施方案中，如果通过加入强脱质子剂(如氢化钠或叔丁醇钾)来合成化合物I a的烯醇盐，则无需再另加酸结合剂。
如果使用酸结合剂，则适宜的物质是常规的无机或有机碱，例如氢氧化钠、碳酸钠、碳酸钾和吡啶。
该反应可在常压或高压下进行，优选在常压下进行。用常规方法进行后处理。
在制备方法(F)中，为得到具有结构(Ie)的化合物，每摩尔化合物(Ia)使用1至2摩尔，优选1至1.3摩尔式(VIII)含磷化合物，反应温度为-40℃至150℃之间，优选-10℃至110℃之间。
可以加入的适宜稀释剂都是惰性的极性有机溶剂，例如醚类、酰胺类、腈类、醇类、硫醚类、砜类、亚砜类等。
优选使用乙腈、三甲亚砜、四氢呋喃、二甲基甲酰胺和甲硫醚。
可以加入的适宜酸结合剂是常规的无机或有机碱，例如氢氧化物或碳酸盐，例如氢氧化钠、碳酸钠、碳酸钾和吡啶。
该反应可在常压或高压下进行，优选在常压下进行。用常规的有机化学方法进行后处理。所得的终产物优选用结晶法、色谱法或所谓“初始蒸馏法”(即真空脱除挥发性组分)进行纯化。
在制备方法Gα中，每摩尔式Ia起始化合物用约1摩尔式(IX)的异氰酸酯进行反应，反应在0至100℃，优选20至50℃下进行。
可以加入的适宜稀释剂都是惰性有机溶剂，例如醚类、酰胺类、腈类、砜类和亚砜类。
适当时，可加以催化剂以加速反应。可以使用的催化剂最好是有机锡化合物，例如二月桂酸二丁锡。该方法优选在常压下进行。
在制备方法Gβ中，每摩尔起始式(Ia)化合物用约1摩尔式(X)的氨基甲酰氯或硫代氨基甲酰氯进行反应，反应在0至150℃，优选20至70℃下进行。
可以加入的适宜稀释剂都是惰性的极性有机溶剂，例如醚类、酰胺类、醇类、砜类、亚砜类和硫醚类。
优选使用二甲亚砜、四氢呋喃、二甲基甲酰胺和甲硫醚。
在一个优选的实施方案中，如果通过加入强脱质子剂(如氢化钠或叔丁醇钾)来制备化合物Ia的烯醇盐，则无需再另加酸结合剂。
如果使用酸结合剂，则适宜的物质是常规的无机或有机碱，例如氢氧化钠、碳酸钠、碳酸钾和吡啶。
该反应可在常压或高压下进行，优选在常压下进行。用常规方法进行后处理。
方法(H)的特征是：使式(Ia)的化合物与金属氢氧化物(XI)或胺(XII)反应。
本发明方法中可使用的稀释剂优选醚类，如四氢呋喃、二噁烷、乙醚；或醇类，如甲醇、乙醇或异丙醇；以及水。本发明的方法(H)一般在常压下进行。反应温度一般为-20℃至100℃，优选0℃至50℃。
进行本发明的方法(H)时，一般使用约等摩尔量的式(Ia)和(XII)或(XIII)的起始物质。但其中的一个成分或另一个成分可以过量较多(至多2摩尔)。一般来说，按照某种方法，通过脱除稀释剂而将反应混合物浓缩。
本发明的式I化合物可用于防治有害生物。有害生物是对植物或高等动物有害的不良有害动物，特别是昆虫、螨和线虫。但有害生物也包括不良植物。
本发明的活性化合物适于防治农业、林业、贮藏产品和材料的保护及卫生领域中所遇到的有害动物，优选节肢动物，特别是昆虫、蜘蛛和线虫。这些化合物具有良好的植物耐性，对温血动物毒性低。这些化合物对通常具有敏感性和抗性的物种有活性，并且对所有或某些发育阶段有活性。上述有害生物包括：
等足目，例如潮虫、平甲虫、鼠妇。
倍足目，例如具斑马陆。
唇足目，例如食果地蜈蚣和蚰蜒属。
肩肩象目，例如庭院么蚰。
缨尾目，例如衣鱼。
弹尾目，例如具刺跳虫。
直翅目，例如东方蜚蠊、美洲大蠊、马得拉蜚蠊、德国小蠊、家蟋蟀、蝼姑属、热带飞蝗、殊种蚱蜢和沙漠蝗。
革翅目，例如欧洲球螋。
等翅目，例如犀白蚁属。
虱目，例如葡萄瘤蚜、绵蚜属、体虱、血虱属和长颚虱属。
食毛目，例如嚼虱属和畜虱属。
缨翅目，例如温室条蓟马和葱蓟马。
异翅亚目，例如扁盾蝽属、红蝽属、方背皮蝽、温带臭虫、长红蜡蝽和蜡蝽属。
同翅目，例如甘蓝粉虱、木薯粉虱、温室粉虱、棉蚜、甘蓝蚜、茶蔗隐瘤蚜、甜菜蚜、Doralis pomi、苹果绵蚜、桃大尾蚜、稠李溢管蚜、微叶蝉属、双叶叶蝉、黑尾叶蝉、麦长管蚜、瘤蚜属、忽布疣蚜、李蜡蚧、油榄黑盔蚧、灰飞虱、稻褐飞虱、红圆蚧、夹竹桃圆蚧、粉蚧属和木虱属。
鳞刺目，例如棉红铃虫、松天蚜、冬天蛾、苹细蛾、苹果巢蛾、小菜蛾、黄褐天幕毛虫、黄毒蛾、毒蛾属、棉潜蛾、桔叶潜蛾、地虎属、刀根虫属、夜蛾属、棉斑实蛾、实夜蛾属、甜菜夜蛾、甘蓝夜蛾、小眼夜蛾、斜纹夜蛾、粘虫属、粉纹夜蛾、苹蠢蛾、粉蝶属、螟属、玉米螟、地中海粉螟、大蜡螟、负袋衣蛾、织网衣蛾、褐织衣蛾、亚麻黄卷蛾、具网卷叶蛾、云松卷蛾、葡萄果蠢蛾、茶长卷蛾、栎绿卷叶蛾。
鞘翅目，例如具斑窃蠢、谷蠢、大豆象、家天牛、赤杨紫跳甲、马铃薯甲虫、辣根猿叶虫、叶甲属、油菜蓝跳甲、墨西哥豆飘虫、隐金甲属、锯谷盗、花象甲属、谷象属、葡萄墨象甲、香蕉根象甲、甘蓝荚象甲、苜蓿叶象甲、皮蠢属、斑皮蠢属、圆皮蠢属、毛皮蠢属、粉蠢属、油菜花露尾甲、蛛甲属、金黄蛛甲、麦蛛甲、拟谷盗属、大黄粉虫、叩甲属、金针虫属、西方五月鳃角金龟、六月金龟和褐新西兰肋翅鳃角金龟。
膜刺目，例如锯角叶蜂属、叶蜂尾、蚁尾、厨蚁和胡蜂属。
双翅目，如伊蚊属、按蚊属、库蚊属、黄猩猩果蝇、家蝇属、厕蝇属、红头丽蝇、绿蝇属、金蝇属、疽蝇属、胃蝇属、虱蝇属、厩螫蝇属、狂蝇属、皮蝇属、虻属、螗蜩属、花圆毛蚊、瑞典麦杆蝇、麦花蝇属、菠菜潜叶花蝇、地中海实蝇、油榄实蝇、欧洲大蚊。
蚤目，如印度客蚤和毛列蚤属。
蛛形纲，如蝎和盗蛛。
蜱螨目，如粗脚粉螨、锐缘蜱属、钝缘蜱属、鸡皮刺螨、茶蔗瘿螨、桔芸锈螨、牛蜱属、扁头蜱属、花蜱属、璃眼蜱属、硬蜱属、痒螨属、皮痒螨属、疥螨属、附线螨属、苜蓿苔螨、全爪螨属和叶螨属。
植物寄生性线虫包括：草地垫刃线虫属、毕肖穿孔线虫、Ditylenchus dipsaci、桔垫刃线虫、异皮线虫属、根结线虫属、滑刃线虫属、长针线虫属、剑线虫属、鬃根线虫属。
此外，本发明的式(I)活性化合物还具有良好的杀真菌活性，可用于防治植物病害，例如防治引起稻瘟病的病原体(稻梨孢)。
作为杀虫剂、杀螨剂和杀线虫剂使用时，本发明的活性化合物在其市售制剂和由这些制剂制得的使用形式中，可以以与其他活性化合物的混合物形式存在，其他活性化合物的例子有：杀虫剂、引诱剂、不育剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节物质或除草剂。杀虫剂包括：例如磷酸酯类、氨基甲酸酯类、羧酸酯类、氯代烃类、苯基脲类和由微生物产生的物质。
本发明的活性化合物在其市售制剂和由这些制剂制得的使用形式中，还可以以与增效剂的混合物存在。增效剂是能增强活性化合物作用的化合物，但所加的增效剂本身不一定有活性。
由市售制剂制得的使用形式的活性化合物含量可在很宽的限度内变化。使用形式的活性化合物浓度按重量计可为0.0000001-95％活性化合物，优选0.0001-1％活性化合物。
它们以适于使用形式的常规方式使用。
本发明的化合物还特别适于处理无性和有性繁殖材料，例如谷物、玉米、蔬菜等的种子，或鳞茎、插条等。
在用于防治卫生有害生物和贮藏产品有害生物时，活性化合物在木材和粘土上显示出显著的残留作用，在石灰基质上显示出对碱具有良好稳定性。
本发明的活性化合物还可用作除草剂，优选用作脱叶剂、干燥剂和阔叶植物破坏剂，特别是除草剂。广义来讲杂草应理解为生长在不当地点的所有植物。本发明的物质是起广谱除草剂还是选择性除草剂的作用，基本上取决于其用量。
本发明的活性化合物可用于下述植物，例如：
双子叶杂草：芥属、独行菜属、猪殃殃属、繁缕属、母菊属、春黄菊属、辣子草属、藜属、荨麻属、千里光属、苋属、马齿苋属、苍耳属、铃兰属、甘薯属、蓼属、田菁属、豚草属、蓟属、飞廉属、苦苣菜属、茄属、焊菜属、水松叶属、母草属、野芝麻属、婆婆纳属、苘麻属、刺果属、曼陀罗属、堇菜属、鼬瓣花属、罂粟属、矢车菊属、车轴草属、毛莨属和蒲公英属。
双子叶栽培作物：棉属、大豆属、甜菜属、胡萝卜属、菜豆属、豌豆属、茄属、亚麻属、甘薯属、蚕豆属、烟草属、蕃茄属、落花生属、芥属、莴芭属、刺瓜属和南瓜属。
单子叶杂草：稗属、狗尾草属、黍属、马唐属、梯牧草属、早熟禾属、羊茅属、蟋蟀草属、臂形草属、黑尾草属、雀麦属、燕麦属、莎草属、高粱属、冰草属、狗芽根属、鸭舌草属、飘拂草属、慈姑属、荸荠属、
Figure C0010194901451
草属、雀稗属、鸭嘴草属、尖瓣花属、龙爪茅属、剪股颖属、看麦娘属和风草属。
单子叶栽培作物：水稻属、玉米属、小麦属、大麦属、燕麦属、黑麦属、高粱属、黍属、甘蔗属、梨属、天门冬属和葱属。
但是，本发明活性化合物的应用决不限于这些属，也可以相同方式扩展应用到其它植物上。
根据使用浓度本化合物适合于全面防治杂草，例如在工业区和铁路、植树或未植树的小路和平地。同样地，本化合物可用于在多年生栽培作物、草坪、草皮和牧草中防治杂草，并可用于在一年生栽培作物中选择性地防治杂草。多年生栽培作物的例子有：人造林、观赏种植林、果园、葡萄园、柑桔林、坚果园、香焦种植园、咖啡种植园、茶园、橡胶种植园、油棕种植园、可可种植园、浆果种植园和啤酒花田。
无论采用芽前或芽后施用的方法，本发明的式(I)化合物都特别适于在双子叶栽培作物中选择性地防治单子叶杂草。
为了防治杂草，本发明的活性化合物本身或其制剂形式，也可以与已知除草剂混合使用，可使用成品制剂或桶混制剂。
用于除草剂混合物的适合除草剂是已知的除草剂，例如：苯胺类，如吡氟草草胺和敌稗；芳基羧酸类，如二氯吡啶甲酸、麦草畏和毒莠定；芳氧基链烷酸类，如2，4-滴、2，4-滴丁酸、2，4-滴丙酸、氟草定、2甲4氯、2甲4氯丙酸和绿草定；芳氧基-苯氧基-链烷酸酯类，如禾草灵、噁唑禾草灵、精吡氟禾草灵、盖草能和喹禾灵；连氮酮类，如杀草敏和达草灭；氨基甲酸酯类，如氯苯胺灵、异苯敌草、甜菜宁和苯胺灵；氯乙酰苯胺类，如甲草胺、乙草胺、去草胺、吡草胺、乙基乙草胺、丙草胺和扑草胺；二硝基苯胺类，如胺磺灵、胺硝草和氟禾灵；二苯基醚类，如氟锁草醚、甲羧除草醚、乙羧氟草醚、氟磺胺草醚、Halosafen、克阔禾和氟硝草醚；脲类，如氯麦隆、敌草隆、伏草隆、异丙隆、利谷隆和甲基苯噻隆；羟胺类，如：枯杀达、稀草酮、噻草酮、稀禾定和肟草酮；咪唑啉酮类，如普杀特、咪草酯、灭草烟和灭草喹；腈类，如溴苯腈、敌草腈和碘苯腈；氧代乙酰胺类，如苯噻草胺；磺酰脲类，如Amidosulfuron、苄嘧黄隆、氯嘧磺隆、绿磺隆、醚黄隆、甲磺隆、烟嘧磺隆、氟嘧磺隆、吡嘧黄隆、赛苯隆、醚苯磺隆和苯磺隆；硫代氨基甲酸酯类，如苏达灭、草灭特、燕麦敌、扑草灭、禾草畏、草达灭、苄草丹、杀草丹和野麦畏；三嗪类，如莠去津、草净津、西玛津、西草净、去草津和特丁津；三嗪酮类，如六嗪同、苯嗪草和嗪草酮；其它类，如氧基三唑、呋草磺、噻草平、恶庚草烷、广灭宁、Clopyralid、燕麦枯、氟硫草定、唑草定、氟咯草酮、草铵膦、草甘膦、异恶草胺、达草止、快杀稗、喹草酸、草硫膦和灭草环。
也可以与其它已知活性化合物混合，这些已知活性化合物如杀真菌剂、杀虫剂、杀螨剂、杀线虫剂、鸟类驱避剂、植物营养物和改进土壤结构的物质。
可以举出下列杀虫剂：
acrinathrin、alphamethrin、betacyfluthrin、bifenthrin、brofenprox、cis-resmethrin、clocythrin、cycloprothrin、cyfluthrin、cyhalothrin、腈二氯苯醚菊酯、溴氰菊酯、esfenvalerate、etofenprox、分扑菊酯、杀灭菊酯、flucythrinate、fluvalinate、lambda-cyhalothrin、二氯苯醚菊酯、pyresmetherin、除虫菊、silafluofen、tralomethrin、zetamethrin；
alaycarb、苯噁威、benfuracarb、混戊威、丁叉威、西维因、巴丹、乙硫甲威、fenobucarb、fenoxycarb、异丙威、甲硫威、乙肟威、metolcarb、草肟威、灭定威、甲丙威、残杀威、叔丁威、thiodicarb、特氨叉威、trimethacarb、二甲威、xylylcarb；
乙酰甲胺磷、谷硫磷-A、谷硫磷-M、溴硫磷-A、cadusafos、三硫磷、毒虫畏、氯甲硫磷、毒死蜱、毒死蜱-M、杀螟腈、甲基内吸磷、异吸磷-II、异一○五九-II、地亚农、敌敌畏、dicliphos、氯线磷、百治磷、乐果、dimethylvinphos、二噁硫磷、乙拌磷、克瘟散、乙硫磷、乙嘧硫磷、杀螟松、倍硫磷、地虫硫膦、安果、庚虫磷、iprobenfos、异丙三唑硫磷、异噁唑硫磷、马拉硫磷、灭蚜硫磷、mervinphos、mesulfenphos、丁烯硫磷、甲胺磷、三溴磷、氧化乐果、砜吸磷、oxydeprofos、对硫磷-A、对硫磷-M、稻丰散、甲拌磷、伏杀硫磷、亚胺硫磷、磷胺、肟硫磷、嘧啶硫磷-A、嘧啶硫磷-M、丙虫磷、低毒硫磷、发果、pyraclophos、打杀磷、喹硫磷、杀抗松、sebufos、硫特普、乙丙硫磷、杀虫畏、双硫磷、二甲硫吸磷、嗪线磷、敌百虫、三唑硫磷、DMTP(O，O-二甲基S-[5-甲氧基-1，3，4-噻二唑-2(3H)-酮基-(3)-甲基]二硫代磷酸酯)、DDVP(磷酸二甲基2，2-二氯乙烯基酯)、CYAP(硫代磷酸O，O-二甲基O-4-氰基苯基酯)；
buprofezin、chlorfluazuron、伏虫脲、flucycloxuron、flufenoxuron、hexaflumuron、pyriproxifen、tebufenozide、teflubenzuron、triflumuron；
imidacloprid、nitenpyram、N-[(6-氯-3-吡啶基)甲基]-N′-氰基-N-甲基乙酰亚胺-酰胺(NI-25)；
abamectin、amitrazin、avermectin、azadirachtin、bensultap、苏云金芽孢杆菌、cyromazine、diafenthiuron、emamectin、ethofenprox、fenpyrad、fipronil、flufenprox、lufenuron、蜗牛敌、milbemectin、pymetrozine、tebufenpyrad、triazuron；
涕灭威、苯噁威、benfuracarb、呋喃丹、carbosulfan、chlorethoxyfos、cloethocarb、乙拌磷、丙线磷、乙嘧硫磷、克线磷、fipronil、地虫硫膦、fosthiazate、furathiocarb、六六六、异丙三唑硫磷、异丙胺磷、甲硫威、久效磷、nitenpyram、草肟威、甲拌磷、肟硫磷、低毒硫磷、pyrachlofos、sebufos、silafluofen、tebupirimphos、tefluthrin、特丁磷、thiodicarb、特氨叉威；
唑环锡、butylpyridaben、clofentezine、三环锡、difenthiuron、乙硫磷、emamectin、fenazaquin、螨完锡、fenothiocarb、分扑菊酯、fenpyrad、fenpyroximate、fluazinam、fluazuron、flucycloxuron、flufenoxuron、fluvalinate、fubfenfox、hexythiazox、ivemectin、甲噻硫磷、久效磷、moxidectin、三溴磷、伏杀硫磷、溴丙磷、pyraclofos、pyridaben、pyrimidifen、tebufenpyrad、thuringiensin、triarathene、4-溴-2-(4-氯苯基)-1-(乙氧甲基)-5-(三氟甲基)-1H-吡咯-3-腈(AC 303630)；
dicotol、乙酯杀螨醇、溴螨酯、杀螨酯、克螨特；
另外，特别有利的混合成分有：
杀真菌剂：
2-氨基丁烷、2-苯胺基-4-甲基-6-环丙基嘧啶、2′，6′-二溴-2-甲基-4′-三氟甲氧基-4′-三氟甲基-1，3-噻唑-5-甲酰苯胺、2，6-二氯-N-(4-三氟甲基苄基)苯甲酰胺、(E)-2-甲氧亚氨基-N-甲基-2-(2-苯氧基苯基)乙酰胺、8-羟基喹啉硫酸盐、(E)-2-{2-[6-(2-氰基苯氧基)嘧啶-4-基氧]苯基}-3-甲氧基丙烯酸甲酯、(E)-甲氧亚氨基-[α-(邻甲苯氧基)邻甲苯基]乙酸甲酯、2-苯基苯酚(OPP)、aldimorph、ampropylfos、敌菌灵、azaconazole、benalaxyl、碘萎灵、苯菌灵、乐杀螨、联苯、bitertanol、灭瘟素、bromuconazole、磺酸丁嘧啶、粉病定、石硫合剂、敌菌丹、克菌丹、多菌灵、萎锈灵、甲基克杀螨、地茂散、氯化苦、百菌清、chlozolinate、硫杂灵、cymoxanil、cyproconazole、cyprofuram、双氯酚、diclobutrazole、diclofluanid、diclomezin、防霉酚、diethofencarb、消螨普、甲嘧醇、dimethomorph、diniconazole、敌螨普、二苯胺、dipyrithione、灭菌磷、二噻农、多果定、腙菌酮、克瘟散、epoxyconazole、乙嘧醇、氯唑灵、双氯苯嘧醇、fenbuconazole、甲呋萎灵、fenitropan、fenpiclonil、fenpropidin、fenpropimorph、薯瘟锡、毒菌锡、福美铁、ferimzone、fluazinam、fludioxonil、氟菌安、fluquinconazole、flusilazole、flusulfamide、flutolanil、flutriafol、灭菌丹、fosetyl-aluminum、稻氨酞、麦穗宁、呋氨丙灵、furmecyclox、双辛胍胺、六氯苯、hexaconazole、甲羟异噁唑、烯菌灵、imibenconazole、iminoctadin、iprobenfos(IBP)、异丙定、稻瘟灵、春日霉素、铜制剂(如：氢氧化铜、环烷酸铜、王铜、硫酸铜、氧化铜、喹啉酮和波尔多液)、双代混剂、代森锰锌、代森锰、mepanipyrim、mepronil、氨丙灵、metconazole、methasulfocarb、甲呋菌胺、代森联、metsulfovax、myclobutanil、福美镍、异丙消、环菌灵、ofurace、oxadixyl、oxamocarb、萎锈散、pefurazoate、penconazole、pencycuron、phosdiphen、稻瘟酞、匹马菌素、哌啶宁、代森联福美锌、多氧霉素、噻菌烯、丙氯灵、杀菌利、百维灵、propioconazole、甲基代森锌、定菌磷、pyrifenox、pyrimethanil、pyroquilon、五氯硝基苯(PCNB)、硫黄粉和硫制剂、tebuconazole、tecloftalam、tecnazen、tetraconazole、噻菌灵、thicyofen、托布津-M、福美双、tolclophos-methyl、对甲抑菌灵、三唑二甲酮、唑菌醇、triazoxide、trichlamid、三苯噻唑、环吗啉、triflumizole、嗪胺灵、triticonazole、有效霉素-A、烯菌酮、代森锌、福美锌。
杀细菌剂：
拌棉醇、防霉酚、氯定、福美镍、春日霉素、octhilinon、呋喃甲酸、土霉素、噻菌烯、链霉素、tecloftalam、硫酸铜和其他铜制剂。
活性化合物可以其本身、其制剂形式或由制剂进一步稀释制得的使用形式使用，如现用溶液、悬浮剂、乳剂、粉剂、糊剂和颗粒剂。它们以常规方式使用，例如泼浇、喷雾、弥雾或散播。
本发明的活性化合物可在植物萌发前或萌发后施用，也可在播种前掺入土壤中。
活性化合物的用量可在很大范围内变化。用量基本上取决于所要求的效果。一般来说，用量在每公顷土壤表面10g至10kg活性化合物之间，优选每公顷50g至5kg活性化合物。
为配制农药，可将本发明的活性化合物制成常规制剂，如溶液剂、乳剂、悬浮剂、粉剂、泡沫剂、糊剂、颗粒剂、气雾剂、浸渍有活性化合物的天然和合成材料，聚合物中的微细胶囊、以及拌种组合物，还可以制成以燃烧装置使用的制剂，如熏蒸筒、熏蒸罐、熏蒸线圈等，以及微量冷雾剂和热雾剂。
根据活性化合物的具体物理性质和/或化学性质，可以把活性化合物制成常规制剂，如溶液剂、乳剂、悬浮剂、粉剂、泡沫剂、糊剂、颗粒剂、气雾剂、浸渍有活性化合物的天然和合成材料、聚合物中的微细胶囊、以及拌种组合物，还可以制成以燃烧装置使用的制剂，如熏蒸筒、熏蒸罐、熏蒸线圈等，以及微量冷雾剂和热雾剂。
这些制剂以已知方式制备，例如使活性化合物与增量剂混合，增量剂是液体溶剂、压力下的液化气和/或固体载体，并任选使用表面活性剂，即乳化剂和/或分散剂和/或成泡剂。在用水作增量剂的情况下，有机溶剂也可用作辅助溶剂。适宜的液体溶剂主要有：芳香烃，如二甲苯、甲苯或烷基萘；氯化芳烃和氯化脂肪烃，如氯苯、二氯乙烷或二氯甲烷；脂肪烃，如环己烷或石蜡，例如矿物油馏分；醇类，如丁醇或乙二醇以及它们的醚和酯；酮类，如丙酮、甲基乙基酮、甲基异丁基酮或环己酮；强极性溶剂，如二甲基甲酰胺和二甲基亚砜；以及水。液化气增量剂或载体是指常温常压下为气态的液体，例如气雾剂抛射剂，如卤代烃及丁烷、丙烷、氮和二氧化碳。适合的固体载体是：例如天然矿物粉，如高岭土、粘土、滑石、白垩、石英、硅镁土、蒙脱土或硅藻土；以及合成矿物粉，如高分散二氧化硅、氧化铝和硅酸盐。颗粒剂的适合的固体载体为：例如粉碎并分级的天然岩石如方解石、大理石、浮石、海泡石和白云石；以及无机物和有机物的合成颗粒、有机物的颗粒，如锯木粉、椰子壳、玉米芯和烟草茎。适合的乳化剂和/或成泡剂为：例如非离子和阴离子乳化剂，如聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚，例如烷芳基聚乙二醇醚、烷基磺酸盐、烷基硫酸盐、芳基磺酸盐以及白蛋白水解产物。适合的分散剂为：例如木质素亚硫酸盐废液和甲基纤维素。
制剂中可以使用粘着剂，如羧甲基纤维素和粉末状、颗粒状或胶乳状的天然和合成聚合物，如阿拉伯胶、聚乙烯醇和聚乙酸乙烯酯，以及天然的磷脂，如脑磷脂和卵磷脂，及合成的磷脂。其它添加剂可以是矿物油和植物油。
可以使用着色剂，如无机颜料，例如氧化铁、氧化钛和普鲁士蓝；有机染料，如茜素染料、偶氮染料和金属酞菁染料；以及微量营养物如铁盐、锰盐、硼盐、铜盐、钴盐、钼盐和锌盐。
制剂中通常含有按重量计0.1至95％的活性化合物，优选0.5至90％的活性化合物。
本发明的活性化合物在其市售制剂和由这些制剂制得的使用形式中，可以以与其他活性化合物的混合物形式存在，其他活性化合物的例子有：杀虫剂、引诱剂、不育剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节物质或除草剂。杀虫剂包括：例如磷酸酯类、氨基甲酸酯类、羧酸酯类、氯代烃类、苯基脲类和由微生物产生的物质。
本发明的组合物除含有至少一种通式(I)化合物及适当的常规增量剂和助剂外，优选含有至少一种表面活性物质。
本发明通式(I)化合物的制备将用后面的制备实施例来说明，其生物活性用后面的生物实施例来说明。
在后面的应用实施例中，将用下列化合物作参比物质：
Figure C0010194901521
(都公开于EP 0,528,156中)
实施例A
烟芽夜蛾试验
溶剂：7重量份二甲基甲酰胺
乳化剂：1重量份烷芳基聚乙二醇醚
为了制备适宜的活性化合物制备物，将1重量份活性化合物与所述量的溶剂和所述量的乳化剂混合，并用水稀释浓缩物至所需浓度。
将大豆枝条浸入所需浓度的活性化合物制备物中进行处理，并在叶片仍然潮湿时用烟芽夜蛾侵染。
经过指定的时间后，测定杀伤百分率。100％表示所有烟芽夜蛾都已被杀死；0％表示没有一只烟芽夜蛾被杀死。
在该试验中，在0.1％的示例性活性化合物浓度下7天后，制备实施例Ib-6、Ib-8、Ic-4和Ic-5的化合物导致100％的杀伤，而先有技术化合物导致不超过40％的杀伤。
实施例B
瘤额蚜试验
溶剂：7重量份二甲基甲酰胺
乳化剂：1重量份烷芳基聚乙二醇醚
为了制备适宜的活性化合物制备物，将1重量份活性化合物与所述量的溶剂和所述量的乳化剂混合，并用水稀释浓缩物至所需浓度。
将用桃芽严重侵染过的卷心菜叶片浸入所需浓度的活性化合物制备物中进行处理。
经过指定的时间后，测定杀伤百分率。100％表示所有蚜虫都已被杀死；0％表示没有一只蚜虫被杀死。
在该试验中，在0.01％的示例性活性化合物浓度下6天后，制备实施例Ic-4和Ic-5的化合物显示出不低于85％的杀伤度。
实施例C
临界浓度试验/根内吸作用
试验昆虫：辣根猿叶虫幼虫
溶剂：4重量份丙酮
乳化剂：1重量份烷芳基聚乙二醇醚
为了制备适宜的活性化合物制备物，将1重量份活性化合物与所述量的溶剂，加入所述量的乳化剂，并用水稀释浓缩物至所需浓度。
将活性化合物的制备物与土壤紧密混合。制备物中活性化合物的浓度实际上并不重要，只有每单位体积土壤中的活性化合物重量(以ppm(＝mg/l)表示)才具有决定作用。将处理过的土壤转移到花盆中，在花盆中植入卷心菜。这样，活性化合物就可以从土壤中被植物根部吸收并输送到叶片中。
为证实根内吸作用，7天后用上述试验动物侵染叶片。再过2天后，通过计数或估计死亡动物数进行评定。活性化合物的根内吸作用由死亡率来推出。如果所有试验动物均被杀死，则根内吸作用为100％；如果仍然存活的试验昆虫的数目刚好与未处理对照一样多，则根内吸作用为0％。
在该试验中，在20ppm的示例性活性化合物浓度下，制备实施例Ic-4的化合物显示出100％的杀伤度。
实施例D
红叶螨试验(OP抗性)
溶剂：3重量份二甲基甲酰胺
乳化剂：1重量份烷芳基聚乙二醇醚
为了制备适宜的活性化合物制备物，将1重量份活性化合物与所述量的溶剂和所述量的乳化剂混合，并用水稀释浓缩物至所需浓度。
取用所有发育阶段的二点叶螨严重侵染的菜豆植株，用所需浓度的活性化合物制备物喷雾。
经过指定的时间后，估测杀伤百分率。100％表示所有叶螨都已被杀死；0％表示没有一只叶螨被杀死。
在该试验中，在0.004％的示例性活性物浓度下14天后，制备实施例Ic-5化合物显示出100％的杀伤度。
实施例E
全爪螨试验
溶剂：3重量份二甲基甲酰胺
乳化剂：1重量份烷芳基聚乙二醇醚
为了制备适宜的活性化合物制备物，将1重量份活性化合物与所述量的溶剂混合，并用含乳化剂的水稀释浓缩物至所需浓度。
取用所有发育阶段的苹果全爪螨严重侵染过的洋李树(约30cm高)，用所需浓度的活性化合物制备物喷雾。
经过指定的时间后，测定活性百分率。100％表示所有苹果全爪螨均已被杀死；0％表示没有一只苹果全爪螨被杀死。
在该试验中，在0.004％的示例性活性物浓度下14天后，制备实施例Ic-4的化合物显示出100％的杀伤度。
实施例F
芽前试验
溶剂：5重量份丙酮
乳化剂：1重量份烷芳基聚乙二醇醚
为了制备适宜的活性化合物制备物，将1重量份活性化合物与所述量的溶剂混合，加入所述量的乳化剂，并用水稀释浓缩物至所需浓度。
将试验植物的种子播入正常土壤中，24小时后用活性化合物制备物浇灌。最好保持每单位面积的水量恒定。制备物中活性化合物的浓度并不重要，只有每单位面积的活性化合物施用量才具有决定作用。3周后，评定植物的损伤程度，以与未处理对照的损伤程度相比的损伤为分比来表示。
数值表示：
0％＝无作用(和未处理对照一样)
100％＝完全杀伤
在该试验中，制备实施例Ia-4、Ib-6、Ib-8、Ic-4和Ic-5的化合物显示出明显优于先有技术的活性和作物选择性。
实施例G
芽后试验
溶剂：5重量份丙酮
乳化剂：1重量份烷芳基聚乙二醇醚
为了制备适宜的活性化合物制备物，将1重量份活性化合物与所述量的溶剂混合，加入所述量的乳化剂，并用水稀释浓缩物至所需浓度。
取5-15cm高的试验植物，以一定的方式用活性化合物的制备物喷雾，从而在每单位面积上施用特定量的所需活性化合物。选择喷雾液的浓度，从而以2000升水/公顷施用特定量的所需活性化合物。3周后，评定植物的损伤程度，以与未处理对照的损伤程度相比的损伤百分比来表示。
数值表示：
0％＝无作用(和未处理对照一样)
100％＝完全杀伤
在该试验中，制备实施例Ia-4、Ib-6、Ib-8和Ic-4的化合物显示出明显优于先有技术的活性和作物选择性。
实施例Ia-1
将16.83g(0.15mol)叔丁醇钾加入100ml无水DMF，0-10℃下滴加入37.10g(0.10mol)2-O-(2，4-二氯苯基乙酰基)降冰片烷-2-羧酸乙酯在100ml无水DMF中的溶液，混合物在室温下搅拌16小时。
后续加工时，反应混合物滴加入500ml 1N盐酸中，沉淀产物吸滤除去后在真空干燥炉中干燥。
产率：29.79g(理论值的92％)白色固体
熔点：227℃。
可类似得到表5所列化合物。
表5
Figure C0010194901581
实施例号    X        Y       Zn      A                     B               m.p.℃
Ia-2        Cl      Cl       H        -(CH2)2-CH(OCH3)-(CH2)2-        220
Ia-3        CH3    CH3    H        -(CH2)2-CH(OCH3)-(CH2)2-        179
Ia-4        CH3    CH3    6-CH3   -(CH2)2-CH(OCH3)-(CH2)2-        220-222
Ia-5        CH3    CH3    6-CH3   
Figure C0010194901582
                 140-145
Ia-6        CH3    CH3    6-CH3   
Figure C0010194901583
                   204-205
Ia-7        CH3    CH3    6-CH3   
Figure C0010194901584
                       217(Z)
Ia-8        CH3    CH3    H        
Figure C0010194901585
                       210
Ia-9        CH3    CH3    6-CH3     
Figure C0010194901586
                 ＞230
表5(续)
实施     X          Y           Zn        A                     B                m.p.
例号                                                                               ℃
Ia-4     CH3      CH3        6-CH3     -(CH2)2-CH(OCH3)-(CH2)2-         187
trans
Ia-4     CH3      CH3        6-CH3     -(CH2)2-CH(OCH3)-(CH2)2-         ＞250
cis
Ia-10    CH3      CH3        6-CH3     -(CH2)2-CH(OC2H5)-                 油
                                           (CH2)2-
Ia-11    Cl        Cl           H          -(CH2)2-CH(OC2H5)-                 204-210
                                           (CH2)2-
Ia-12    CH3      CH3        H          -(CH2)2-CH(OC2H5)-                 172-182
                                           (CH2)2-
Ia-13    CH3      CH3        6-CH3     -(CH2)2-CH(O-n-C3H7)-              172-175
                                           (CH2)2-
Ia-14    CH3      CH3        6-CH3     -(CH2)2-CH(O-n-C4H9)-              油
                                           (CH2)2
Ia-15    CH3      t-           H          -(CH2)2-CH(OCH3)-(CH2)2-         150-165
                    C4H9
Ia-16    CH3      t-           6-CH3     -(CH2)-CH(OCH3)2-(CH2)2          206-210
                    C4H9
Ia-17    CH3       CH3        6-CH3                       218-220
实施       X        Y       Zn      A                B                  m.p.
例号                                                                     ℃
Ia-18      Cl      Cl      H                       223
Ia-19      CH3    CH3    H                       240-242
Ia-20      CH3    CH3    6-CH3    -CH2-CH(SCH3)-(CH2)3-         245-247
Ia-21      CH3    CH3    6-CH3    -CH(OCH3)-(CH2)4-              油
Ia-22      CH3    CH3    6-CH3    -(CH2)2-CH(CO2C2H5)-         165-180
                                      (CH2)2-
Ia-23      CH3    CH3    6-CH3    -(CH2)2-CH(CO2H)-(CH2)2-     ＞250
实施例Ib-1
Figure C0010194901611
将3.25g(10mmol)化合物Ia-1加入40ml无水二氯甲烷中，加入1.42g(14mmol)三乙胺和一满刮勺DMAP，再滴加0.94g(12mmol)乙酰氯在20ml二氯甲烷中的溶液，混合物室温下搅拌16小时。
后续加工时，反应混合物用柠檬酸水溶液、NaHCO3水溶液和NaCl水溶液洗涤，干燥后在旋转蒸发器中蒸发。经硅胶快速层析而进一步提纯，其中用环己烷/乙酸乙酯(3∶1)。
产率：1.70g(理论值的46％)固体
熔点：126℃
可类似得到表6所列化合物。
表6
Figure C0010194901621
实施例号    X            Y       Zn         A                      B             R1                   m.p..℃
Ib-2        Cl          Cl       H         -(CH2)2-CH(OCH3)-(CH2)2-        -CH3                  Oil
Ib-3        Cl          Cl       H         -(CH2)2-CH(OCH3)-(CH2)2-        -t-C4H9              Oil
Ib-4        CH3        CH3    H         -(CH2)2-CH(OCH3)-(CH2)2-        -CH3                   Oil
Ib-5        CH3        CH3    H         -(CH2)2-CH(OCH3)-(CH2)2-        -t-C4H9               134
Ib-6        CH3        CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-        -CH3                   Oil
Ib-7        CH3        CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-        -i-C3H7               Oil
Ib-8        CH3        CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-        -t-C4H9               78-80
Ib-9        CH3        CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-        -C-(CH3)2-CH2Cl      113-115
Ib-10       CH3        CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-        -CCH3(CH2Cl)2        118-120
Ib-11       CH3        CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-        -CCH3(CH2OCH3)2     103-104
表6(续)
实施例号 X        Y       Zn         A                      B          R1                 m.p..℃
Ib-12    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-         106-107
Ib-13    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-    -C2H5               Oil
Ib-14    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-            Oil
Ib-15    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-    -C(CH3)2C2H5     107-108
Ib-16    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-    -C(CH3)2i-C3H7   94-96
Ib-17    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-              Oil
Ib-18    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-             Oil
Ib-19    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-    
Figure C0010194901635
         200-202
Ib-20    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-    -CH2-t-C4H9        126-129
表6(续)
实施例号 X        Y       Zn         A                      B           R1                          m.p..℃
Ib-21    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-      -C6H5                      Oil
Ib-22    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-      -CH＝C(CH3)2               107-108
Ib-23    CH3    CH3    6-CH3    -(CH2)2-CH(OCH3)-(CH2)2-      
Figure C0010194901641
   Oil
Ib-24    CH3    CH3    6-CH3   
Figure C0010194901642
                  t-C4H9                      Oil
Ib-25    CH3    CH3    6-CH3   
Figure C0010194901643
                    -CH3                         76-78
Ib-26    CH3    CH3    6-CH3                        -i-C3H7                     Oil
Ib-27    CH3    CH3    6-CH3   
Figure C0010194901645
                    -t-C4H9                     114-116
表6(续)
实施例号 X        Y       Zn           A              B       R1          m.p..℃
Ib-28    CH3    CH3    6-CH3                 -CH3        188-189
Ib-29    CH3    CH3    6-CH3   
Figure C0010194901652
             -t-C4H9    131
Ib-30    Cl      Cl      H                 -t-C4H9    112
Ib-31    CH3    CH3    H                 -CH3        105
Ib-32    CH3    CH3    H     
Figure C0010194901655
           t-C4H9     Oil
Ib-33    CH3    CH3    6-CH3 
Figure C0010194901656
          -CH3        159
表6(续)
实施例号 X        Y       Zn           A                   B       R1                     m.p..℃
Ib-34    CH3    CH3    6-CH3     
Figure C0010194901661
          -i-C3H7                104
Ib-35    CH3    CH3    6-CH3     
Figure C0010194901662
                -t-C4H9                102-103
Ib-36    CH3    CH3    6-CH3     
Figure C0010194901663
                -C(CH3)2-CH2Cl       111
Ib-37    CH3    CH3    6-CH3     
Figure C0010194901664
           -C(CH2Cl)2CH3        136
Ib-38    CH3    CH3    6-CH3     
Figure C0010194901665
           -C(CH2-O-CH3)2CH3  119
Ib-39    CH3    CH3    6-CH3     
Figure C0010194901666
           -C(CH3)2-C2H5      105
Figure C0010194901671
Figure C0010194901681
Figure C0010194901691
Figure C0010194901701
实施例Ib-42顺式
实施例Ib-42反式s
将3.16g(10mmol)化合物Ia-4加入40ml无水二氯甲烷中，加入1.42g(14mmol)三乙胺和一满勺DMAP，再滴加1.38g(13mmol)丁酰氯在20ml二氯甲烷中的熔液，混合物室温下搅拌16小时。
后续加工时，反应混合物用柠檬酸水溶液、NaHCO3水溶液和NaCl水溶液洗涤，干燥后在旋转蒸发器中蒸发。经硅胶快速层析分成异构体，其中用环己烷/乙酸乙酯(6∶1)。
产率：0.92g(理论值的24％)无极性反式异构体和0.21g(理论值的5％)极性顺式异构体。
熔点：分别为85-87℃和125-126℃。
实施例Ic-1
将3.25g(10mmol)化合物Ia-1加入40ml无水二氯甲烷中，加入1.42g(14mmol)三乙胺和一满勺DMAP，再滴加1.47g(12mmol)氯甲酸异丙酯在20ml二氯甲烷中的溶液，混合物室温下搅拌16小时。
后续加工时，反应混合物用柠檬酸水溶液、NaHCO3水溶液和NaCl水溶液洗涤，干燥后在旋转蒸发器中蒸发。用MTB醚/正己烷重结晶而进一步提纯。
产率：2.84g(理论值的69％)固体
熔点：136℃。
可类似得到表7所列化合物。
表7
Figure C0010194901721
 实施例号  X  Y  Zn  A  B L  M R2  m.p.℃
 Ic-2  Cl  Cl  H -(CH2)2-CH(OCH3)-(CH2)2- O  O -i-C3H7  100
 Ic-3  CH3  CH3  H -(CH2)2-CH(OCH3)-(CH2)2- O  O i-C3H7  Oil
 Ic-4  CH3  CH3  6-CH3 -(CH2)2-CH(OCH3)-(CH2)2- O  O -CH3  Oil
 Ic-5  CH3  CH3  6-CH3 -(CH2)2-CH(OCH3)-(CH2)2 O  O -i-C3H7  Oil
 Ic-6  CH3  CH3  6-CH3 -(CH2)2-CH(OCH3)-(CH2)2- O  O -i-C4H9  Oil
 Ic-7  CH3  CH3  6-CH3 -(CH3)2-CH(OCH3)-(CH2)2- O  O -s-C4H9  Oil
 Ic-8  CH3  CH3  6-CH3 -(CH2)2-CH(OCH3)-(CH2)2- O  O -C2H5  Oil
Figure C0010194901731
Figure C0010194901741
实施例Id-1
先向3.16g(10mmol)烯醇Ia-4的40ml无水CH2Cl2溶液中加入1.52g(15mmol)三乙胺，然后于0-10℃滴加1.48g(13mmol)CH3SO2Cl在10ml CH2Cl2中的溶液。
混合物室温搅拌2小时，然后用柠檬酸水溶液(10％)和NaHCO3水溶液洗涤，干燥后蒸发。
之后将粗产物与20ml石油醚混合，吸滤后干燥。
产率：2.40g(理论值的61％)固体
熔点：155℃
可类似得到表8所列化合物。
表8
Figure C0010194901781
Figure C0010194901782
实施例Ie-1
Figure C0010194901791
向2.2g化合物Ia-4的10ml四氢呋喃溶液中加入1.1ml三乙胺后再加1.42g(0.007mol)乙烷硫代磷酸丙基硫醚。混合物50℃下搅拌3小时后蒸发，剩余物经硅胶层析，其中用己烷/乙酸乙酯/丙酮(30/10/1)作为洗脱剂。得到2.1g(理论值的62％)粘性油状题示化合物(异构体混合物)。
1H-NMR(300MHz，CDCl3)：δ＝2.19，2.20，2.25，2.26(4s，9H，苯基- CH 3)，3.15-3.25，3.57(2m，1H，CH-OCH3)，3.33，3.39(2s，3H，OCH3)，6.87(s，2H，苯基- H)ppm
31P-NMR(162MHz，CDCl3)：δ＝119.05，119.64ppm。
可类似得到表9所列化合物。
表9
Figure C0010194901801
实施例号   X   Y   Zn   A   B   L   R4   R5   NMRδ(ppm)
  Ie-2cis   CH3   CH3   6-CH3   -(CH2)2-CH(OCH3)-(CH2)2-   S   C2H5   s-C4H9-S-   3.39(s，3H，OC H 3)，3.15-3.2(m，1H-CHOCH3)
  Ie-2trans   CH3   CH3   6-CH3   -(CH2)2-CH(OCH3)-(CH2)2-   S   C2H5   s-C4H9-S-   3.32(s，3H，O CH 3)，3.57(m，1H， CH-OCH3)
  Ie-3cis   CH3   CH3   6-CH3   -(CH2)2-CH(OCH3)-(CH2)2-   S   CH3   H7C3-S-   3.9(s，3H，O CH 3)3.18-3.23(m，1H，C HOCH3)
实施例号 X  Y  Zn  A  B  L  R4 R5 NMRδ(ppm)
Ie-3trans CH3  CH3  6-CH3 -(CH2)2-CH(OCH3)-(CH2)2-  S  CH3 H7C3-S- 3.33(s，3H，OCH3)，3.57(m，1H，C HOCH3)，6.87，6.89(s，2H，Ar- H)
实施例II-1
Figure C0010194901821
实施例II-2
18.40g(0.10mol)2-羟基降冰片烷-2-羧酸乙酯和24.59g(0.11mol)2，4-二氯苯基乙酰氯在100ml无水甲苯中回流16小时后，混合物在旋转蒸发器中蒸发。得到37.10g(定量)油状题示化合物。
可类似得到表10所列化合物。
表10
实施例号 X Y Zn A B R8 m.p.℃
  II-2   Cl   Cl   H   -(CH2)2-CH(OCH3)-(CH2)2-   C2H5   Oil
  II-3   CH3   CH3   H   -(CH2)2-CH(OCH3)-(CH2)2-   C2H5   Oil
  II-4   CH3   CH3   6-CH3   -(CH2)2-CH(OCH3)-(CH2)2-   C2H5   Oil
Figure C0010194901841
Figure C0010194901861
实施例号  X  Y  Zn  A  B R8  m.p.℃
II-22  CH3  CH3  6-CH3 -(CH2)2-CH(CO2C2H5)-(CH2)2- C2H5  Oil
II-23  CH3  CH3  6-CH3 -(CH2)2-CH(CO2H)-(CH2)2- C2H5  Oil

Claims (2)

1.式(II)化合物：
Figure C001019490002C1
其中
X、Y和Z每一个代表C1-C6烷基或卤素
n代表0-3的数，
A和B与其连接的碳原子一起形成饱和或不饱和3-8元环，该环可被C1-C6烷氧基取代，或
A和B与其连接的碳原子一起代表C3-C8元环，该环中两个取代基与其连接的碳原子一起代表饱和C5-C7环，该饱和环可任选被C1-C6烷基，C1-C6烷氧基或卤素取代并且可被氧间断，
R8代表烷基。
2.根据权利要求1所述式(II)O-酰基-α-羟基羧酸酯的制备方法，其特征在于：
a)将式(X III)2-羟基羧酸(酯)用式(X IV)苯基乙酰卤酰化并任选酯化：
其中R12代表氢或烷基，
A和B定义同权利要求1，
其中X，Y，Z和n定义同权利要求1，
Hal代表氯或溴，或
将式(IIa)羟基羧酸酯化：
Figure C001019490003C2
其中A，B，X，Y，Z和n定义同权利要求1。
CN00101949.XA 1993-09-17 2000-01-31 O－酰基－α－羟基羧酸酯类化合物及其制备方法 Expired - Fee Related CN1216030C (zh)

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CN1292375A (zh) 2001-04-25
JP3427857B2 (ja) 2003-07-22
CN1103642A (zh) 1995-06-14
US5719310A (en) 1998-02-17
EP0647637A1 (de) 1995-04-12
ES2127859T3 (es) 1999-05-01
HU9402666D0 (en) 1994-12-28
AU7159994A (en) 1995-03-30
CN1061040C (zh) 2001-01-24
JPH07179450A (ja) 1995-07-18
US5610122A (en) 1997-03-11
BR9403768A (pt) 1995-05-16
GR3029455T3 (en) 1999-05-28
IL110946A0 (en) 1994-11-28
EP0647637B1 (de) 1999-01-27

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