JPS6183181A - Herbicide thiophenesulfonamides and pyridine sulfonamides - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION US Patent No. 4.59a959, issued to Levltt on Aug. 16, 1983, discloses herbicidal thiophenesulfonylureas such as;

On June 10, 1981: Issue stone f”L 7j Yo 1
:+7 A% correction issue 5α142 discloses, for example, a tD removal 1:L agent-based thiophenesulfonylurea tablet.

Wood patent 4゜37 issued on April 5, 1983
B-991f', for example, discloses O-phenylsulfonylureas such as B-991f'.

European Patent Application No. 84975, published on July 20, 1983, and European Patent Application No. 83.476, published on August 10, 1983, contain the formulas [where Q is various 5- and 6- Discloses herbicidal benzenesulfonamides which are negative, saturated, unsaturated heterocyclic rings.

South African patent application 83/8416 (May 1, 1984)
2) is the formula [wherein AFi is unsaturated or only partially saturated 5- or 6
--membered heterocyclic ring system, which is attached via a carbon atom and contains 1.2 or 5 heteroatoms and 01-C, alkyl, Cl-C4 haloalkyl, C1-C, Al; xy, C, -C, alkylthio, C, -C, alkoxyalkyl, so(cs -C4
The present invention discloses herbicidal sulfonamides of (alkyl)amino, halogen, cyano or nido;

Formula [wherein R1 is B, C1, Br, F, 0l-C4 alkyl, C
, -C, Al:xy, C, -C, alkylthio, No!
4fc is CO, R, and Oυ, and R, is l(, CI,
The herbicide pyridine sulfonamides of Brmaji wa CH3 are patented by Yoroku A! ! 15.480.

Yorotsu/? The special rod 55,895 has the formula [wherein, R1 is S (0) n Rs, and R1 is H,
C1, F XBr −, CHi, OCHL, CF, .
NOI, CN"rfc discloses herbicidal pyridi/sulfonyl amides of NH,.

The European Patent Specification m85975 and the European Patent Dependency 55.476 describe herbicidal benzenesulfones of the formula: Amides are disclosed.

US Patent 437 R9? 1i″i, formula [in the formula, R is especially phenyl, and RIFiH, FSCl, Br-, No! , CFt.

C1-' C37 #k, OCF, or c, -c.

Alkoxy] discloses herbicidal benzenesulfonamides.

European #patent issued on December 28, 1983! 97,122 has the formula [wherein,
Furkylsulfonyl, halogen, No, , CWR,,
So, NR, R, or COR] herbicidal sulfonamides.

South African Patent Application 83 to 639 is of the formula [wherein X is 0, s, so, So, or XA can form an amino group NR, R, and R1 is H1
C, -C, alkyl, C, -C, alkoxy/, C,
-C, haloalkyl, C, -C, haloalkoxy, Ct
-Cw alkoxyalkoxy, C, -C! Alkylthio, C, -C, alkylsulfinyl or fc is C, -C.

6 alkylsulfonyl) discloses herbicidal sulfo/amides.

The present invention provides novel compounds of 2fa-1e, agriculturally suitable compositions containing them, and general or i7i selective pre- and post-emergent herbicides or plant growth regulators. This article concerns how to use them as agents.

In the formula, P, [H, fcltCf, 1, nl''Uo, 1 or 2, W is 0 or S, Q l-4 phenyl ring, or sulfur, oxygen, or a saturated 5- or 6-membered ring containing 1 heteroatom selected from the group consisting of O-1 sulfur, O
-Choose from 1 oxygen or O-S@ smart element 1
- an unsaturated 5- or 1-membered ring containing 6 heteroatoms; in compounds of formula 1 -re Q is optionally SR, C, -C, alkyl, C5-C+ fulkenyl ,
CI-"1 haloalkyl, halo", CI -CX alkokino, C, -C, alkylthio, C, -C, alkenylthio, Cj-C, alkenyloxy, C, -C,)-
Corekoxy, cl-C! hacoalkylthio, C, -C
, alkylthio, C, -C, cyanoalkylthio, C+
+-CI alkoxycarbinylmethylthio or 9 1f selected from C, C, alkylcarbonylmethylthio
In the compounds of formula Id and le, Q (g optionally Cl-C4 alkyl,
HaO) f 7, C1-C, alkenyl, C, -C.

Alkoxy, Cs-Cs7, kylthio, C, -C.

alkenylthio, c, -c, haloalkoxy or C,
-C, , may be substituted with one or more groups selected from haloalkylthio, E is H, C1-C2 fulkyh, C1-C27 alkoxy, halogen, No, , C
,-Ct haloalkyl, C,-brialkylthio, C,
-C, alkylsulfonyl, Cr-Ct flukoxycarbonyl, c, -c, soalkylamine sulfamoyl, E+ F: rHSCI, Br, CHI 9 is 5CHs, A (vin A-2 -6 X is H, c, -c, alkyl, C1-C, alkoxy,
C, -C4 haloalkoxy, CbiC4)10 alkyl,
C, -C, haloalkylthio, C, -C, alkylthio, halogen, cl-c.

Alkoxyalkyl, CI-C, alkoxyalkoxy, amino, C1-C5 alkylamino or so(C1-
Cs alkyl) amino υ, 'Y is H, CI-C
4 alkyl, C1-C4 alkoxy, C, -C, haloalkoxy, C, -C, noroalkylthio, C, -C,
alkylthio,
C, -C, alkylamino, di(C, -Cs alkyl)
Amino, cl-C4 alkenyloxy, C, -C, alkynyloxy, C2-C, alkylthioalkyl, CI
-C, alkylsulfinylalkyl, ct-Cgfurkylsulfinylalkyl, CI-C, haloalkyl, C
,-C.

Schiff o Furkyl, C, -C, alkynyl, [(0)
R is ε, m is 2 and Fis is R, L, two is 0 or S″t′, RI
L and J are P, then c, -c, alkyl, Rc is [or CH, 2 is CH or NT, J is 0 to Yl: cu, X, is C) I, , OCR, , QC, H, or OCF
, H), Y, is H'l YicI(, and X, is CHsSOCRl or SCH, and Y, is C)(s, CHzCHs or C)
, and X is CH3 or OCR, and X4 is C1(s, OCH,, QCtH,, CI, F
.

B r, I, OCF! H, CHIF, 0CR2CH
2F.

OCR, CHF! , OCR, CF, or CF,
, Y4 is)(,%CH,,OCH,,QCtH,,CHy
OCHs, NHCH,, N(OCRs) CKs, N(
CHs) g, CH, CI, , CF,, SCH,, OC
HtCH=CHz, OCKICmiCH.

○H,QC,H,,OCH,CH,0CHs,CH,S
CH,, [(o) aes Re Dust with Re or cyclopropyl, provided that 1)
H,,OCF,HSNH,,NHC5,,N(OCR
s) CHs or N (CIs)! Ashi, and Y
4 is OCH3,0CyH@, OCF, H, NHCH3
, N (0CRs) CHs must be N(CHx)t, 2) The total number of carbons in Q must be 8 or less, 5) X,
Y, Sometimes it is attached to the thiophene or pyridine ring via a carbon; 5) In compounds of formula Id and Ie, Q is 1) i-1,
When it is 2,4-triazol-1-yl,
Z is cH, and 6) Y is cyclopropyl;
IcI-m, X4 is C1, F-s B r i 7
c is 617 other than engineering, and 7) When W is S and 8, R is H″r, AFiA
-1 is used, J is J-1, and Y and Y4 are CH,, OCH,, D C, H,, CHt OCHs,
C, H,, CF,, S CHs , OCHt CH=C
Ht, OCHz C=CH-OCR, CH, QC mountain,
In the above definition of CM (OCHs), the term "alkyl" used alone or in compound terms such as "alkylthio" or "alkylj" refers to straight or branched alkyl, For example, methyl, ethyl, n-
Propyl, inpropyl/L- or various butyl isomers.

Alkoxypymetogi-n 〒ni-shichi,'/ --IJ
+-, J-ruoxy, inpropyloxy or various butoxy isomers.

Alkenyl is a straight-chain or branched alk/group, e.g.
T-vinyl, 1-propenyl, S-probel, 'f
77” H4 nilma fc is various butenyl isomers,
shows.

Alkynyl #'i linear or branched alkyne a,
9KJjc-Ff X fnyl, 1-propynyl, 2-
7'ropinyl or the three butynyl isomers.

Cycloalkyl refers to cycloterovir, cyclobutyl or cyclotetraethyl, in a single form or, for example,! =#-fr
``Ha; Gun'' used in the 8th post-containment of ``H Furkyl J'' indicates fluoroA1, bromine, bromine, and iodine.

Alkylcarbonyl 177 ceter also represents 1;p;pionyl.

7 le v + 7/'J le c nyl indicates methoxy force rubinirma or ethoxy force rubi ni kkf.

Methylsulfonyl 27'fCFi to alkylsulfonyl
Minitylsulnyl*, alkylthio, alkylamine, alkylsulfamoyl, etc. are similarly defined.

For example, in the expression Ct-Cs alkylthioalkyl, the number of carbon atoms indicated is meant to define the total number of carbon atoms in the substituent. For example, C! -C, alkylthioalkyl is CHtSC) (,,CH,SC C,H,,
CH, CH, S CH, or CH (CHz) S C
Hs and C,-C,alkoxyalkoxy is OCH,OCR,,0(CHz) 40
CHs also F′i0 CIt O(CHt ) sCI
s and the various structural isomers subsumed therein.

Relatively high herbicide activity, relatively large plant growth regulator activity, and/or relatively easy synthesis are preferred for the refinement of stones = 1) Q is 92'', □ Q Q-4Q-5Q-6 Q -7Q -9 & Q-10, Q-11Q-12 Q-15Q-14Q-15 Q-16Q-17Q-18 Q-19Q-'OQ-21 R3' Q-25Q -26Q-27 Q-28Q-29Q-50 ---1----■------■-1-----Q-6
I Q-5'4 Q-S5g -37
Q -s s Q -39Q-40Q-4i
i! R3, R1 is I(, SC1, CH3 or 0CHs, R
2) (SF-, C1-, CHs, OCHI or C
Fs, R4, R6, R1, R3, R, and RIO are independently H, 7c is CHt, n' is 0 or 1, R, l are H, 5H1c, - C, alkyl, C1-C.

Alkylthio, C5-C, alkenylthio, Cs -C
4-Ataquinylthio, C, -C, cyanoalkylthio, S
CHt COtCHs, S CHtCOt C2H!
, 5CHt [(0)CH,, halogen, c, -csfurukoki/1fcItiOCHyCH= 8 at Hz, B,' is HSCI (,, C1 or Br, W/ is 0 or sr, W' is 0 , S or NR11'''C filter, R11 is HS
C, -C! Alkyl or C)(, C' shame C1(.

Compounds of the formula ra-re: 2, E is H, A is A-1], X is C)1. ,OCH,,QC,H,,CI or B
r-0, Y is H, CH3, OCHg, CIH1,0CtH@,
CHIOCR3, CFs , OCFtHs Cycloglopipro OCH, CF, , NHCHs , N (CHs)t
, CH (OCRs) t "t7?, j h' is O, and R, / and H, t are independently H, CH, or C1, R is H, and W is Preferred compounds of ring 1, where O is: 5) Preferred compounds of ring 2, where o is O'''C; 4) Y is CY-C! Preferred ring 3 compounds, represented by alkyl, OCR, or ocp2a; 5) Preferred ring 4 compounds, in which R1 is H), R2 is H or C1, and 2 is CH; 6) Formula Preferred compounds of ring 5 of Im; Preferred compounds of ring 5 of formula 1b; 8) Preferred compounds of ring 5 of formula 1e; 9) Preferred compounds of ring 6, where Q is Q-1: 10)Q
Preferred ring 6 compounds, wherein Q is Q-2; 11) Q is Q-2;
5, preferred ring 6 compounds D: 12) Compounds of preferred term B, where Q is Q-5: 15 Preferred ring 6 compounds, where Q is Q-7; 14) Q is Q -10, preferred compounds of ring 6; 15) preferred compounds of ring 6, where Q is Q-11; 16) compounds of preferred term B, where Q is Q-15; 17) preferred compounds where Q is Q-11; Preferred ring 6 compounds where Q-16; 18) Preferred ring 6 compounds #1 where Q is Q-20;
9) Preferred ring 6 compounds, where Q is Q-26; 20)
Preferred compounds of ring 6, where Q is Q-28: 21) Compounds of preferred ring 6, where Q is Q-36; 22) Q is Q-
39, preferred compounds of ring 6; 23) compounds of preferred item 7, where Q is Q-1; 24) Q is Q-2;
Preferred compounds of ring 7; 25) Preferred compounds of ring 7, where Q is Q-5; 26) Preferred compounds of ring 7, where Q is Q-5; 27) Q is replaced by Q-7. , preferred compounds having ring 7; 28) preferred compounds having ring 7, where Q is Q-10; 2
9) Preferred ring 7 compounds where Q is changed by Q-11: 50]
Compounds of preferred ring 7, where Q is Q-15; 31) Preferred compounds of ring 7, where Q is Q-16; 62) Q is Q-
20″T: Or, preferred compounds of ring 7; 33) Q is Q-
Preferred ring 7 compounds are 25; 34) Q is Q-28;
35) Preferred compounds of ring 7, where Q is Q-56; 56) Q is Q-59,
Preferred compounds of ring 7; 37) Preferred compounds of ring 8, where Q is Q-1; 38) Preferred compounds of ring 8, where Q is Q-2; 69) Q is Q-5. , preferred compounds having ring 8; 40) preferred compounds having ring 8, wherein Q is Q-5; 41
) Preferred ring 8 compounds, where Q is Q-7; 42) Preferred ring 8 compounds, where Q is Q-10; 43) Preferred ring 8 compounds, where Q is Q-
11; Preferred ring 8 compounds; 44) Q is Q-15;
Preferred compounds having ring 8; 45) Preferred compounds having ring 8, in which Q is Q-16; 46) Q is Q-20;
Preferred compounds of ring 8; 47) Preferred compounds of ring 8, where Q is Q-25; 48) Preferred compounds of ring 8, where Q is Q-28
Compound knowledge of; 49] Preferred compounds of ring 8, where Q is Q-56; 50) Preferred compounds of ring 8, where Q is Q-59; 31) Preferred compounds of ring 16, where w' is S Compounds; 5
2) Preferred ring 30 compounds, where W' is S; 55) W
' is S, suitable ring 44 compounds; 54) F- is I (, W is O, Q is Q-49Q-5o Q-51 Q-5s Q-56Q-37 R1!Q -58Q-59Q-60 Q-64Q-63Q-66 Q-73Q-74Q-75 and phenyl, with n' as defined above, and approximately 1tsR1
! and R14 is independently Ht or CH, H, CHs, C, H,, C, -C, 7/L/
+ A/ Chit, S C'H, CH=CH2, SCF,
) iXOCH, Saitake OCR, CH, and R76 is Ht or C1, Ru2. and R1, are independently H, CH, or OCR
.

, R8 and R1° are independently CH3 or OCR, W" is O,S-length FiN R+ +, and RI
I is as defined above, 55) J is J
-1, E, is H, n' is 0, and Q is Q-46, Q-47, Q-48, Q-49, Q-5
2, Q-53, Q-54, Q-55, Q-56, Q-5
9, Q-61, Q-62, Q-63, Q-66, Q-6
7, Q-69, Q-72, Q-75, Q-78, Q-8
2, Q-83 and phenyl; 56) X is CH,,0CHs, ocH, CH3 or C1 and Y4 is CH,,CH,C) (,,OCH,,CH(0C
Hs) t Violet is (:') (, OCR, Preferred compounds with ring 55; 5, 7) Preferred compounds with ring 56, where n is 0; 5
8) Preferred ring 37 compounds, wherein Y is CH, CH, CH, or OCR; 59) Preferred ring 58 compounds of formula Id; 60) Formula I
Preferred compounds of ring 58 of e; 61) Preferred compounds of ring 59, where Q is Q-46; 62) Preferred compounds of ring 59, where Q is Q-47; 63) Q is Q-48 64) Preferred compounds of ring 59, where Q is Q-49; 63) Preferred compounds of ring 59, where Q is Q-52; 66) Q is Q- 67) Preferred ring 59 compounds, where Q is Q-54; 68) Preferred ring 59 compounds, where Q is Q-55; 69) Preferred ring 59 compounds, where Q is Q-55; -56, preferred ring 59 compounds; 70) Preferred ring 59 compounds, where Q is Q-59; 71') preferred ring 59 compounds, where Q is Q-61; 72) Q Preferred compounds of ring 59, where Q is Q-62 3) Preferred compounds of ring 59, where Q is Q-63; 74) Preferred compounds of ring 59, where Q is Q-66; 75) Preferred compounds of ring 59, where Q is Q-67; 76) Preferred compounds of ring 59, where Q is Q-69; 77) Preferred compounds of ring 59, where Q is Q-72; 78) Compounds of preferred item 59, where Q is Q-75; 79) Compounds of preferred item 59, where Q is Q-78; 80) Compounds of preferred item 59, where Q is Q-82; 81 ) Compounds of preferred item 59, where Q is Q-83; 82) Compounds of preferred item 59, where Q is phenyl; 83) Preferred item J 60 O compounds, where Q is Q-46; 84 ) Preferred item 6(1) compounds where Q-47 exists; 83') Preferred item J 60(7) where Q-48 exists
Compounds; 86) Compounds of preferred item 6 (1) where Q is Q-49; 87) Compounds of preferred item 60O where Q is Q-sz; 88) Preferred item where Q is Q-53; Compounds of Tancho 60; 89) Compounds of preferred item 60, where Q is Q-54; 90) Compounds of preferred item 60, where Q is Q-55; 91) Q is Q-56 , the compounds of preferred item 60; 92) the compounds of preferred item 60, where Q is Q-59; 93) the compounds of preferred item 60, where Q is Q-61; 94) the compounds of preferred item 60, where Q is Q-62; 95) Compounds of preferred item 60, where Q is Q-63; 96) Compounds of preferred item 60, where Q is Q-66; 97) Q is Q-67 Compounds of preferred item 60, where Q is Q-69-c; 99) Compounds of preferred item 60, where Q is Q-72; 1oo) Q is Q -75; 101) Compounds of preferred item 60, where Q is Q-78; 102) Compounds of preferred item 60, where Q is Q-82; 103) Q is Compounds of Preferred Item 60, which is Q-83; 104) Compounds of Preferred Item 60, where Q is phenyl; the highest deodorant activity, the greatest plant growth regulator activity and/or the most cunning Particularly preferred for ease of new synthesis are: N-[(4,5-dimethylpyrimidin-2-yl)aminocarbonyl)-3-(inxacy-3-yl)-2- Thiophene sulfonamide, melting point 172.5-173°C, φ3-(inxacy-3-yl)-N-[(4-methoxy-6-methylpyrimidine-2-yA/)aminocarbonyl-2-thiophenesulfonamide , melting point 19
2℃ (decomposition), ・N-[(4,6-Simethoxypyrimidin-2-yl)
Aminocarbonyl)-3-(inxasil-3-yl)-2-thiophenesulfo/amide, melting point 137-1
5g'C1 @3-(s-chloro-IH-1,2,4-)lyazol-1-yl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-thiophenesulfonamide , melting point 204-205°C (decomposition), ・N-[(4-methoxy-6-methylpyrimidine-2-
yl) ami7carbonyl-3-(lH-pyrrole-1-
yl)-2-thiophenesulfonamide, melting point 152-
155°C, -N-[(4-methquin-6-methyl-1,3゜5-triazin-2-yl)aminocarbonyl-3-(l)I
-pyrrol-1-yl)-2-thiophenesulfonamide, melting point 144-146°C, -N-[(4,6-dimethoxypyrimidin-2-yl)
7? /carbonyl)-3-(xH-pillow A, -1
-yl)-2-thiophenesulfonamide, melting point 14
2-146°C, ・N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-(IH-pyrrol-1-yl)
-2-thiophene sulfonamide, melting point 170-173
°C, ・N-C, (4,s-dimethyl-1,3,5-)riazin-2-yl)aminocarbonyl:l-3-(IH-pyrrol-1-yl)-2-thiophenesulfonamide) ”
, 8 points 153-156°C, ・N-[(4,s-dimethoxy-1+3+5-triazin-2-yl)aminocarbonyl]=3-(1H-pyrrol-1-yl)-2-thiophenesulfonamide, MIA156 159℃, N
-[(4-di0-6-methoxypyridimin-2-yl)ami/carbonyl]-3-(IH-pyrrol-1-yl)-2-+offenesulfonamide, melting point 146-1
49°C, @N-[(4-methoxy-6-methylpyrimidine-2-
yl)aminocarbonyl'3-3(2-methyl-4-thiazolyl)-2-thiophenesulfonamide, melting point 14
6-149℃.

・N [(4,6-cymethoxypyrimidin-2-yl)
Aminocarbonyl]-3-(2-methyl-4-thiazolyl)-2-thiophenesulfonamide, melting point 164-1
68°C, and ·N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl:]-2-(IH-1
.

2.4-)Riazol-1-yl)-3-pyrimidinesulfonamide, mp 235-238C.

Compounds of Synthetic Formula 1-7c can be produced by Method I above IPi shown in Reaction Schemes 1 to 4. These steps are equally applicable for the preparation of compounds of formulas ld and Ie.

Many of the compounds of Formula I can be prepared by reaction of a sulfonamide of Formula 2 with a suitable methyl carbamate of Formula 3 in the presence of at least equimolar amounts of dimethylaluminum according to Scheme 1.

Reaction Scheme I These reactions #i are carried out at 25° to 40° C. under an inert atmosphere and in an inert dipolar aprotic solvent such as methylene chloride for 10 to 96 hours. Details of this reaction as well as the preparation of carbamates of formula 3 are described in European Patent Publication No. 13.480CP.

Many of the compounds of Formula 2 can also be prepared by reacting a sulfonyl carbamate of Formula 4 with a suitable complex amine of Formula 5 according to Scheme 1.

Reaction formula 1 This reaction is carried out according to European Patent Publication No. 44807.
It is carried out in a solvent such as 1,4-dioxane at 0 DEG to 100 DEG C. for 0.5 to 24 hours. The necessary carbamates of formula 4' are prepared by reacting the appropriate sulfonamide with carboxydiphenyl in the presence of an equimolar amount of a string base such as sodium or potassium hydride.

Some of the compounds of Formula 1 can also be prepared as shown in Scheme 2.

Reaction formula 2 [wherein, Y' is CH,, C, I (or CH, CF)]
This series of reactions is described in European Patent Publication No. 30,140.
and the necessary two-six heterocyclic isonanoates were prepared according to the process disclosed in Swiss Patent No. 379.
,062, U.S. Pat. No. 3,919,228, U.S. Pat.
, 732, 223 and U, Fono Zhitskyi (O
izycki)'s Angeva/De-\Mii International Edition in Iggritsch (A
ngew, Chem, Int, Ed, Engl.
), 1976.10% 402 and 403.

Compounds of Formula I can also be prepared by the reaction of deenylsulfonyl isocyanate with a suitable heterocyclic amine as shown in Scheme 3.

Scheme 3 The reaction of Scheme 3 is most successfully used when carried out in an inert diprotic aprotic solvent such as methylene chloride, tetrahydrofuran or acetonitrile at temperatures between 208 and 80°C. can. If the main product is insoluble in the reaction solvent, simple filtration can be used to
If the product is soluble it can be isolated by evaporation of the solvent, for example trituration with a solvent such as 1-chlorobutane, diethyl ether or methanol, and filtration.

As shown in reaction formula 32, the chenylsulfonyl isocyanates of No.
It can be prepared from sulfonamides of formula 2 by the method described in 21. On the other hand, these sulfonyl isocyanates are prepared by (1) 1 mole of sulfonamide 2 using n-butyl isocyanate in a solvent such as 2-butanone or acetonitrile in the presence of a base such as potassium carbonate. It can also be synthesized by a two-step process consisting of reaction with phosgene in refluxing quincine as solvent. This method is based on New Methods of Preferable Organic Chemistry (N
ewer Methods of Preparation
i-ve Qrganrc Chernjstry)
”, W, Force) (Forest), Ed, Volume ■,
Academic Press, New York, 1967.22
The manufacturing method is the same as that described on page 3-241. Reaction formula 3b shows the process.

Reaction formula 3a Reflux! - Kinlen - Reflux Dab. . ■ In the formula, W is O] The sulfonyl inthiocyanates of 28, where ~■ is S, are K, Hortke's Alkib del.
Fermatsui Land Berichtedel.

Do (7chi x (Arch, Pharm,), 299, 1
74 by treating sulfonamides of formula 2 with carbon disulfide and aqueous potassium dispersion and then reacting the dipotassium salt with phosgene.

Compounds of formula I are also obtained by the process described in South African Export No. 830441 and illustrated by Scheme 4. laf 1,8-diazabicyclo(:5.4.0:)-undec-7-ene (DBU)
is added to the reaction mixture, the chenyl sulfonamides of formula 2 are combined with the heterocyclic carbamates of formula 10 to 1.2
- React in dioxane at 20c' to 80°C for 1 to 24 hours. The resulting product is isolated by diluting the reaction mixture with water, acidifying and then filtering. Heterocyclic carbamates of formula 10 can be represented by reaction formula 4a
is synthesized by reacting the heterocyclic amines of formula 5 shown in pyridine with diphenyl carbonate or phenyl chloroformate in pyridine at a temperature within the range of 20° to BO°C.

Scheme 4 % Formula % Scheme 4a The synthesis of thienylsulfonylureas of formulas 7a-7c relies on the necessary intermediates, thiophenesulfonamides of formula 2, while pyridine sulfonyls of formulas Jd and le The synthesis of ureas relies on the intermediate pyridine-sulfonamide of formula 196 below.

Some of the intermediate sulfonamides of Formula 2 above can be prepared from amines of Formula II in a two-step process as shown in Scheme 5/. This is (Sa)+t
and campling the diazonium salt with sulfur dioxide to produce the sulfonyl chloride of formula 12, and amination with (5b) ammonium hydroxide or anhydrous ammonia to produce 2. .

Reaction formula 5 % Formula % The reaction of reaction formula 5a is carried out by adding a bath solution of amine 11 in a mixture of @hydrochloric acid and glacial vinegar to 15° with an aqueous solution of sodium nitrite.
It is applied by processing at ~5°C. Approximately 0℃
After stirring for 10 to 30 minutes at 20° C. to ensure completion of the diazotization, the solution is dissolved in glacial acetic acid with an excess of sulfur dioxide and the catalyst Violet Chloride (1) or Chloride (II). to the mixture at about 10°C. The temperature is maintained at about 10°C for -1 hour, then increased to 20°-30°C and held at that temperature for 2 to about 24 hours. This solution is then poured into a large amount of ice water.

The sulfonyl chloride 12 can be isolated by filtration or by extraction in a solvent such as ethyl ether, methylene chloride or suitably Fi1-chlorobutane and subsequent evaporation of the solvent.

The amination described in the reaction of Scheme 5b above is
A solution of sulfonyl chloride 12 is treated with at least 2 molar equivalents of anhydrous ammonia at -20° to 30°C in a solvent such as ethyl ether or methylene chloride.
It can be easily implemented by If the sulfonamide product 2 is insoluble, it is dissolved in a monolayer by filtration and subsequent salt washing with water. If product 2 is soluble in the reaction bath, it can be isolated by separating the precipitated ammonium chloride and evaporating the solvent.

Many other sulfonamides 21 can be prepared by reaction of the corresponding sulfonyl chloride 12 with excess aqueous ammonium hydroxide in tetrahydrofuran at 0 DEG to about 40 DEG C. over a period of 0.5 to 10 hours. The sulfonamide product 21' is isolated by evaporation of the tetrahydrofuran solvent, addition of water to the residue and filtration.

On the other hand, the intermediate product sulfonyl chloride 12 can be produced as shown in Reaction Scheme 6 below.

Reaction formula 6 According to reaction formula 6, S, N, Bha-t
tacharya), C, Earbo:y (Ear
born) and R, I~1. War/Yu (~'v
(c) (J, Chem.

Soc, (C)), 1968.1263'! and H,
Quast) j, ; and F, key (
5ynthesis 1974.489 in ether.

The reaction between ]3 and n-butyllithium at about -70°C yields g! The Mated lithium salt was added to sulfuryl chloride in hexane at about -30° to -20°C and
The sulfonyl chloride 12 is formed by stirring for 0.5 to 10 hours at 30°C to 30°C. Subsequent reaction of 12 with ammonia or ammonium hydroxide as described above provides the corresponding sulfonamide.

Starting with a suitable bromothiophene and formula 6
Using simple modifications of the process steps described in 1999, one skilled in the art can prepare some of the other sulfonyl chlorides of formula 12' above. If necessary, this reaction is limited to cases where the substituent (CH,) Q is inert to the lithium reagent under the reaction conditions, as will be obvious to those skilled in the art. For a general description of metallization using lithium reagents, see HoW, Gsch
wend) 2 and H, R, Rodrigu
ez) (D Organic Reactions (Org
, 几actions) 1979.26.1.

Certain sulfonamides are best prepared by the process of Scheme 7 below.

Reaction formula 7 Production of sulfinate salts 14 by the process of reaction formula 7 1-
Known in the art; see US Pat. No. 4,127,405 and H8W, Gu/Yuend et al., cited above. Sulfonamides 2 are best prepared by treatment of sulfine salts with chloramines. In this step, a suspension of salt 14 in ether is prepared at a low temperature (25 to -30
℃) with a dry ether solution of chloramine. Reactants for minutes or hours? 'I worship it. After filtration, the reaction mixture was washed with aqueous bisulfite,
Dry and remove the solvent on a rotary evaporator. The crude product is further purified by conventional methods such as crystallization or chromatography.

In the method shown in reaction formula 8, the chenyl-
Copper compounds are dissolved in a solvent such as pyridine or quinoline with an aodo or bromoheterocycle (X(CH,) Q ,
[(wherein X is I or Br and n is 0, 1 or 2)].

Copper compounds of formula 15 are prepared by reacting the corresponding lithium compounds with cuprous iodide or cuprous bromide in a solvent such as diethyl ether. Detailed procedures for this type of reaction are described in the references below.
, 1970.24.2379-2388;
hem, 5cand, ), 1972.26.3383-
33136° Reaction Scheme 8 i As shown in Reaction Scheme 9, the compound of Formula 16 is treated with an acid catalyst in an alcoholic solvent or trifluoroacetic acid to remove the t-butyl group to form compounds of Formula 2. generate.

Reaction Scheme 9 In the above synthesis, the general definition of the compound of formula (■) is (C'
) (ri. is meant to contain a Q substituent, and the sulfonylurea functionality corresponds to 1g of the three possible combinations defined in the gist of the invention as formula 1, lb or d). It will be convenient to use this general formula below in this disclosure for the purpose of simplifying and clarifying this teaching.

QX nX n', R, R,, R2, R5, R, /, R
1′, R,, R,, R6, R,, R,, R,, Rlo,
R, , , n', W, W/, W", A, X, Y and zli are as described in the summary of the invention unless otherwise specified.

Heterocyclic thiophene sulfonamides of formula 2 are important starting materials for the preparation of compounds of formula 1 of the present invention, and individual examples are prepared by method 1 below.

In the particular case where Q is Q-1 and n is O,
Compound 17 can be prepared by the reaction sequence shown in Reaction Scheme 10.

Reaction Formula 10% Formula % In this synthesis step, 1-phenylpropyne of formula 18 is made into a full fat using an excess base. Attachment with divalent carbon gives a phenyl-substituted ketene dithylate, which undergoes intramolecular cyclization to give 19 after proton loss. The conditions necessary for this conversion are R, L, P, deE7g (p
eJong)'j6 and Brandsma
Journal of Organometallic Chemistry (J, Organometal, Chem,
), 1982.238, C17tC.

Mild oxidative chlorination of 19 gives the sulfonyl chloride of formula 20, which is converted to the sulfonamide 27 by treatment with ammonia in THF solution at temperatures between -35° and 25°C.

On the other hand, 17 can also be produced by the process of reaction formula 11.

3-Phenylthiophe/21 is 2 in diethylnithyle
Reaction with n-butyllithium for 0.5 hours at 5° C. produces a lithiated intermediate, which can be quenched using sulfnol chloride. The resulting sulfonyl chlorides 29 and 2(1,1) were then treated with ammonia in the <T)-IF melt as described above to give 1
7 and isomer 2. The desired 17 can be isolated by those skilled in the art using known chromatographic techniques.

21 metallization 1-iR, Teardi' = (Tardi
ni), G, Multi IJ (Martelli), P,
Spa-gnolo and M. Cheno)
(Jiecko) Journal of the Chemical Society (J.

It is written. See Reaction Scheme 13 for further details.

Scheme 11 Other intermediates that can be used are known in the art. 2
- phenyl-3-bromothiophene (Q-1, n is O) can be prepared by the acta of N, Gjoca and S, Gronowitz,
3-bromo-2,2'-bithiophene (Q-2, W' is S and n is O) and 3-bromo-2,
3′-bithiophene (Q 3,” is S, n is 0
For example, S., Gronowitz, J., Skremstad and B., E.
riksson)'s Arkib 7 or Chemi (Ark,
kemi) 1.967.28.99.

When n is 1 or 2, organocopper methods known to those skilled in the art are applied to produce substituted thiophenes of Formula 21, as shown in Scheme 112A. That is, ditheonyl S'M') tium of formula 21b can react with alkyl halides of formula H to produce 1,
Conversion to sulfonamide '17b can be carried out by the method shown in Reaction Scheme 11.

Reaction formula 11 types 21 types 17b Isomer compound of formula 17b with general structure of formula 2b and 2C @Asahikawa has 2,3-dibromo-; or 3.4-
A chemical method similar to Kisaragi's Scheme 113A using dibromothiophene will provide the required middle rBJ main paraboloids. 3-(2-furanyl)- and 3-
This paper describes the synthesis of (2-chenyl)thiophenes.

Reaction formula 12 Eto H, Wynbeg, A, Logothetis and Verploeg
)'s The Journal Off the American Chemical So? If-f I (J, Am, Chem, Sa
c.) 1937.1, 2-lithiofuranio or 2-lithiothiophene is added to 3-ketotetrahydrotheofe/in diethyl ether at a temperature of 0 DEG C., according to the work described by 1972. The reaction was quenched and distilled from sulfur to give 3-substituted dihydrothiophenes of formula 22, which were converted to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). and dehydration to give formula 23. These theophenes can be selectively metallated at the 2-position and converted to sulfuryl chloride in hexane solution to form sulfonyl chlorides of formula 24H, which can be converted into T)I It is converted to the desired sulfonamide 24 by treatment with ammonia in P solution.

For cases where n is 1t or 2, the process of Scheme 12 can be followed by starting with ./tons of Formula 200 (commercially available or obtained by methods obvious to those skilled in the art). A similar process can be used; ultimately compounds of formula 24b will be produced.

R1 4b Starting with the appropriate 3-substituted thiophene and following the metallization step shown in Scheme 12 or a simple modification thereof, one skilled in the art can Sulfonamides can be produced.

Only 3-substituents that are inert to the gold-plated layer reagent I with respect to the desired 2-metalization of the thiophene nucleus are suitable for this synthetic method, and such substituents can be determined by a person skilled in the art.
It should be obvious.

Supplementing the metalation-sulfonation step illustrated by Scheme 12, a similar metalation-sulfination can be performed to provide sulfonamides of Formula 2a. The latter step is described by Scheme 13 and is entirely similar to that of Scheme 7.

Reaction formula 13: When the sulfinate of Nimi is produced, they are reduced to 0.
0H0:1)-yb=p:y (CnIeman) and C1R, Hauser, The Journal of the American Chemical Society (J
, Am, Chem, Soc, ), 1928.50
．． Direct conversion of sulfonamides 22I can be achieved by reaction with polylamins such as those described by E. No. 1193. The sulfinates of formula
Brown)'s The Journal Off Organic
Chem7,) Rii O, Org, Chem, ), 195
4.19.894: W, E, Toru (Jru
ll) O and E, Wclisch
The Jah Chill Off The American Chemical
Sopuyeti 51777 and Y, K, Urieb (Y
uriev) Oyobi N, K, Sadabaya (Sad
avaya) Nojarf Ruoff General Chemistry Off the Knee x Su x 7.7-tv (J
0gen, Chem, USSR), 1964.3
4.1814 to give the sulfonyl chloride and the sulfonyl chloride can also be converted to 2a by treatment with ammonia in an ethereal solvent such as THF. Both of these steps are compatible with the sulfinic acid groups of Formula 14 generated by Reaction Scheme 7.

Use of the method of Scheme 7 indicates that the metallation of the 3-# substituted thiophene of Formula 25 at the 2-position is (CH,
)nQ[of particular interest in those cases where this is not possible due to the reactivity of the exchange. The formation of 2-brominated thiophene 27 allows the use of very facile mild halogen-metal exchange conditions as shown in Scheme 14.

Reaction Scheme 14 The electrophilic aromatic odor accumulation of the 3-substituted thiophenes of Formula 25 results in S, Gro-10wits.
z), P. Moses and Man, B.

Alkip of Hornfeldt
As shown in the teachings of Ark, Kem, 1962, et. Sulfinization with sulfur dioxide gives the appearance of a sulfinate salt, or sulfonation with sulfuryl chloride gives sulfonyl chloride 28.

If (CHI)nQ provides most of the coughophile addition, (CHt)nQ can be placed in the 3-position of the thiophene nucleus after the sulfonamide moiety, or the same synthesis can be performed in the 2-position. You can also add The entire reaction process is shown in Equation 15.

2.3-Dibromothiophene 29Fi is preferably lithiated at the 2-position and treated with sulfuryl chloride to give the sulfonyl halide 30. Treatment with tertiarybutylamine leads to the tertiary-butyl protected sulfonamidation of formula 31. The second lithium
The logen exchange reaction allows the addition of a substituent (CI-I or nQ), which can be added as such or in a synthetically equivalent structure.

Following the general teachings of Schemes 12-15, sulfonamides of Formula 2a can be prepared in the following manner.

Amounts of the compound of Formula 35 can be prepared using the reaction sequence shown in Reaction Scheme 16.

Reaction formula 16 3(3-furanyl)- and 3-(3-chenyl)-2-bromothiophenes h, Y of formula 33.

Tamura, Y, Yoshimi
) and Z, Yoshida's Tetrahedran, 1979.3
5.329 or a similar modified method. By the method of Reaction Scheme 4, sulfonyl chlorides of formula 34 and the resulting sulfonamide chlorides 35 are obtained.

C. Acta-chemi-Scandinahi force of Urenius (
Acta Chcm, 5cand, ) 1972.
26.3383 and 4. Nirnon and C. Urenius's Acta Chemiforce Scandinavia (AClaC)
hem, 5cand, ), 1970.24.2379
As shown in reaction formula 17, using the process
-3, W'=OX n=Q) can be produced. For cases where n is 1 or 2, a modification similar to Scheme 17 using the appropriate furanyl copper material may be used to form the desired chenyl bromide of Formula 37a. Sulfonamide B containing groups (Q-4, Q-s, Q-
6, ~”'= Os S )i”t&EE 18 Middle 1
c It can be produced by catalytic reduction of the corresponding furanic or theofunine compounds as shown.

Reaction formula 18 Reaction formula 18r is shown! Select ゛ for the type you are using -s''
L elements are known from the literature. ,,Catalyst, 4-1 sister, pressure and temperature for reduction of furan were determined by Samuel 5evadesh's Furan Xf.
j (The Furans)”, A, , P, Dunlop i6 and F, N, Pe
ters), Reinhold Publishing Corporation, New York, N.Y., June 1953.
74-7t3 pages; and P, N, Rylander (Ryl
and) cr) - Catalytic hydrogenation in organic content (
Catalytic Hydro-generation
Reduction of thiophenes 1-LH,D as described in 1979, p. 227-234.

Hartough's Thiophene and its attractant Q
1) e-rivatives)”, The Science of Heterocyclic Humpounds Series, Interscience Publications, Inc., New York, January 6, 1952.
It is written on pages 7-169.

The compound of 842 can be produced as shown in reaction formula J9A1.

Reaction formula 19 % formula % 4 0 In formula 42 According to reaction formula 19, lithiothiophene is -78° ~ OU
In this example, frO of Tl-1F is reacted with lactone L in an ethereal solvent to produce lactol 43. Lactol can be dehydrated using a strong force such as sulfuric acid to produce a thiophene of formula 44. 44
On-
The reactants are quenched and cooled to give lithium sulfinates of formula 45, which can be lithiated using Bunaoctalithium and diethyl ether as solvent at a temperature of about 0° C.
It is made into a single by the 7-- older brother of the reaction 7'↓tI+. Sulfinate? Treated with chloramine to transform τ42
oo Selective hydrogenation as desired to produce compounds of formula 46 (
R, -H), □ is generated.

3-(2-tetrahydrofuranyl)-2 and 3 of formula 46
-(2-tetrahydropyranyl)thiophenes can also be prepared as shown in Scheme 20.

Reaction Scheme 20 Reaction formula 47 is obtained by reacting nothiothiophene with 1-78° to 25°C in an inert solvent such as TJ-]F.
0 Tuba O aldehyde force "+" is reacted to give chenyl alkoxide η, which undergoes molecular ρ reaction to form cyclic 1
- Tellurium '148 has been lost. These 1 reaction formula 13
was converted to the sulfonamide ν46 by the method of give. Treatment of 49 with chloramine provides colossal compound 46.

The sulfonamides of Formula 50 are prepared in a manner similar to that of Scheme 12, as shown by Scheme 21.

Reaction formula 21 [wherein, lithionophene reacts with the ketones of formula to give tertiary alcohols of formula 51 after proton disappearance. Dehydration of 51 using a strong acid such as trifluoroacetic acid produces compounds of formula 52 as double bond isomers, which are reductively hydrogenated to give 53, N-bromosuccinic acid. Bromination using imide in vinegar for about 1 hour at room temperature produces bromides of formula 54, and these bromides tIP undergo a rogen-metal exchange as described in Scheme 1. sulfonamide μ of formula 50
,give.

The compound of formula 56, yM (Q 7, n is 0), is prepared as shown in reaction scheme 22 (reaction of the sodium salt of virol with bromothiophene sulfonamide using oxidized brocade in DNI P). It can be manufactured by

Scheme 22 Alternatively, 2-aminothiophene-3-sulfonamide is prepared as shown in Scheme 23 and reacted with 1,4-dicarbonyl compounds to provide substituted compounds of Formula 60. You can also do that.

Reaction formula 23 % Formula % J, G, Lombardion
The Journal of Organic Chemistry (J, Org, Chem,), 1971, 36.184
Similar to the teachings of Section 3, the Tasha IJ--bunarsulfonamide of formula 37 is treated with 2 equivalents of n-butyllithium in tetrahydrofuran at 50 DEG to 80 DEG C. to give the dilinao salt. JA4. +) - Dee (P, e
edy) and V, :2. Smeck-us
) of Tetrahydrone Letters (Tetrahe-dr
on Left, ), 1983.3795, 58 was treated with tosyl azide and then treated with sodium hydride to give aminothiophene sulfonamide 5.
Give 9. Coupling with a 1,4-dicarbonyl compound provides a compound of formula 60. The 1-butyl group t-removal gives the free sulfonamide.

V, Effi, hi, Cugnode 8evricourt,
S, Rault and 8-1, lo
bba) Nohe 5-.

Heterocycles, 1981.
16.1519, 3-(1-pyrrolyl)thiophene 61 can be synthesized. Then sulfonamide 6
The conversion to 2 is depicted in Scheme 24.

Reaction formula 24 Choice of 61
J LτSumako with a temperature of about 0° to 25°C 1'9 jc E
(r '' T: I Ill, 'f 1811 (m) in red, generate the compound of 263 hk.

Using the method described in Reaction Equation 14, T)(
Halogen-gold exchange in F at -78°C followed by quenching with sulfur dioxide gives sulfy7kr lithium 64.

Next, the chloramine was aminated with chloramine to give the sulfonamide I11 of formula 62.

Compound of formula 61 #2y
Follow b'w ”:'i] to die.

1b, 1b3 and 61 can be converted to the sulfonamide of formula 62a by the method of reaction formula 24.

62;I Thiophene of formula 70 (Q-9, n is 0) can be prepared as shown in Scheme 26.

Reaction formula 26 The round table reaction of reaction formula 26 is well known in the art, and A,
l, Nyoons””S)g and o, P, Bean)ff- Chemistry of Virols ('l'h
eChae-mistry of Pyruoles)
”, Academic Zures, = Knee a-'7, N, Y
, l 977 out of 1 kokiza n. 3-(l in formula 71
-methyl-pyrrol-3-yl)-thiophenes can be synthesized according to Reaction Scheme 27.

Reaction Scheme 27 In a reaction similar to Reaction Scheme 12, lithiothiophene reacts with 1-methyl-3-pyrrolidinone 72 in THE solution at -78° to 0°C to form tertiary alcohol 73. 73 for example,
--Dehydration with a strong acid such as refluoroacetic acid to produce dehydration products of formula 74 as a mixture of regioisomers.

Dehydrogenation of (1) with sulfur in hot DMF produces 71. Compounds of Formula 71 are each converted to sulfonamides of Formula 75 by the method steps of Scheme 14.

I-1 of this research: A method of producing sulbone 7' Midono JJ, which is a 1:1 interstitial compound, is possible.
Many i! of Q in each one-body arrangement! , the same is true for Taste TC.

When the synthetic method of a fatty species is applicable to all the necessary isomers, it may be convenient to use the following general formula herein.

In the general synthetic method below, the use of X' and other substituents on the thiophene group at positions not specified requires that the indicated be in the adjacent position and that when X' is in the 2-position it is hydrogen. When present and in the 3-position, it means bromine.

A formula showing the production of a certain type of (5-inxazolyl)thiophene (Q-10, 'A'/I=S, 0 is .) of Formula 76 is shown in Reaction Scheme 28. .

Reaction Scheme 28 In formula 5, X'ti2-) (or 3-B'), lithiothiophene is reacted with acyl chloride in THF solution at a temperature of -78° to 25°C to produce ketones of formula B. These ketones are dissolved in dimethylalkanamide dimethylacetate in a solvent such as toluene or DMF at a temperature of 500 to 140°C for 3 to 24 hours.
to produce the β-amino α, β-unsaturated ketone μ of formula 7B. For details on the rise of this Jr., please see the Technical Info.
Acetals 1, Aldrich Chemical Company, December 1973, 7 (Lin) and S.A. Lang (I, ang)
Off Organic Chemistry (J, Org.

Chem.), 1980, 45.4837. 78 for example ethanol-based or water-based].

Treatment with hydroxylamine hydrochloride in a solvent such as 4-dioxane at a temperature of 25° to 100° C. for 1 to 48 hours and product 76 isolated by addition of water to the reaction medium and extraction in methylene chloride. do. Similar process is Y
, IJ N and S1, Rand's Journal Off.
Heterobic click chemistry (J, Hcter
ocyl, Chem, ) 1977, ] 4.345
Written by IL. Compound of formula 76 DAμ Reaction formula 13
It can be converted into suitable sulfonamides of formula 79 by step 0.

For cases where n is 1 or 2, a modification of Scheme 2B can be used to produce sulfonamides of Formula 79a. Equation 282 illustrates this variation.

Scheme 28a The appropriate lithiothiophene is reacted with the second alkyl bromide to provide the formula 77AC tininyl catalyst. Ketones of formula 77b are degenerated by ketal exchange using acetone and anhydrous copper (■), and they are converted to formula 7 in exactly the same manner as described above for reaction scheme 28.
The compound of formula 76d, which is converted into the ink solvent of 61f, is converted into the appropriate sulfonamide of formula 79a by the step of Reaction Scheme 13; Ofni 7m (Q
-10;
W'=S1nF'i1 and id2) is the reaction equation 29
In a similar manner as shown in a! I leave in A-built.

Reaction formula 29 % formula % [In the formula, 09-30 in methylene
treated with phosphorus oxychloride for 0.2 to 2 hours at 0.2 to 2 hours, and the sodium persalt in the pumped water was 0.0 to 10 °C.
The perchlorates of Formula 81 are formed by adding the perchlorates over a period of 0.2 to 1 hour. Thereafter, 81 is sulfurized in DMF and water at 0' to 10°C for 0.2 to ] hours.
to develop. Finally, these thiophenes are reacted in methanol at a temperature of 20 DEG to 30 DEG C. for 0.2 to 1 hour with hydroxy/ruamine--sulfonbutyric and 2 equivalents of pyridine to give 80. The preparation of thiophenes of the formula 14cQ=Q-11, kV'1jNRI+theal) and 83 (Q=Q-10, 'vV/' is NR, ), which can be performed by Teoff, is shown in Reaction Scheme 30. .

Reaction equation 30 α of equations 78 and 78a from equations 28 and 28a
, β-Fugenwa chloride can be reacted with hydrazines in refluxing ethanol for 1 to 16 hours.

Product mixture #' of thio7enes of formulas 84 and 83
J11 was separated by the chromatography method of Kimiyu technology expert. , 84 man 7 mi door [intermediation to 1;
Ii:i7: )12 catties - Te1,] -1→ Jko,
Shintake is done by the method of υ with 1).

Reaction formula 31 is written as the brother of Anaguchi's 3-(3-inxazolyl)thiphene λ.

3-Chenylaldehyde reacts with hydroxylamine salt solution 9a in ethanol to produce the oxime 288. These oximes are N-ri0-succinic acid imide (
NC8) to produce chlorides of formula 89, which, when reacted with vinyl acetates in the presence of 1 mole s5 of triethylamine, are addition-cyclized to produce acetates of formula 90. 90 is converted to thiophenes of formula 91 by oxidizing off the acetic acid in hot DBU.

Conversion of formula 92 to sulfonamide 3A can be accomplished by overuse of the chemical method described by equation 13, equation 32 of l shin T1! ':l: Indicates a method for producing 3-(3-promonaenyl)isoxazole of formula 93.

Reaction formula 32 [Shiki Ko, "s" J4].

1-74 to reaction IZL of reaction formula 32 (1, anell
a) Other Chim.

Ind, ) (Milan), 1963.47.996 and G, Gaudiano et al.
It is carried out by a process similar to that taught by M, Ital, ), 1959.89.2466. That is, 3-bromo-2-thiophenehydroxam chloride of formula 94 was dissolved in tetrahydrofuran from 0 to 30
React with a suitable acetylenic Grignard reagent for 1 to about 16 hours at <0>C. The product is isolated by addition of water and ammonium chloride and chloride using chile/chloride. Acetylenic Grignard reagents are prepared from substituted acetylenes by processes described in the cited literature.

Another method for preparing compounds of Formula 93 is shown in Scheme 33.

The reaction of the above reaction formula 33 is G, Bianna Etsute (Eia
nchetti) Other Kazetuta ummica Italia-f
(Oazz, Chim, Ital, ), 196
3.93.1714 by the same steps as those described in 3.93.1714. That is, in Reaction Scheme 33, 94 is reacted with triethylamine and N-alkenylmorpholine in chloroform under reflux for 0.2 to about 1 hour to form 5-(N-morphorino') of Formula 95.
The inxazolyl converted to -3- is then reacted with 10% hydrochloric acid under reflux for about 0.2-0.5 hours to produce 93. Product 93 is isolated by extraction with methylene chloride.

To my colleague, +1. Micetich 7 Canadian Journal of Chemistry
), the reaction of hydroquibum chloride with vinyl acetate instead of enamine produces the compound of formula 93.

(3-inchazolyl)thiophenes of formula 96 can be prepared according to reaction scheme 34.

Reaction Scheme 34 %Formula % In Reaction Scheme 34, 7 anotiofe/ is reacted with about 5
Mononitriles of formula and can be produced by reaction with the appropriate alkylnitrile and sodium over a period of ~25 hours. Similar conversions have been made to U.S. Patent λ479.363, Dutch Patent 6,60094 and T.
o), S, Nakagawa, J, Okumura, K, Takahashi
shi), K, w y, ka (Afa-suka)
) and Y, Narita's Priten・
-60°C to 80°C in methylene chloride in the presence of an amount of potassium hydroxide
can be reacted with hydrogen sulfide in a sealed vessel for 24 to 96 hours to provide iminothionamides of Formula 98. Such reactions 1'iT, Naitu, S, Nakagawa and K.

Takahashi Chemical and Pharmaceutical
Preten (Chem, P arm, Bwl l, )
, 1968.16.148 and 1. Joe press (g
oe-rdeles) and B, rl! - Land (po and )'s hemitsunoko・herichte (Ch, e
It is comparable to the study of M, Ber, ), 1961.94.2950. Compounds of the formula, gloss''- are cyclized by treatment with boromine in ether, chloroform or ethanol solution using potassium carbonate as base at 20° to 40° C. for 0.5 to 4 hours to produce the above. References Dutch Patent A60'8,094 and J. Joppler and H. Borland, Ang, Chem., 1962, et. 1.77. . M, Beringet, B, prijs
) and 11, x Relais 7 Meyer (Erlenm
eyeer ) (7) Helvetica stain power acta (
Ilelv-Chim.

4), 1966, -(''-12466), soil was diazotized with nitrous acid generated in situ, and the resulting diazonium salt was oxidized at O'C for 2 hours with 50 chili powder. (H), followed by optional selective metallation and alkylation to yield 1. Conversion to the corresponding 6-sulfonamide 100 is carried out using the synthetic method described in Scheme 13. Ru.

As shown in Reaction Equation 35 below, formation (Q
-12, W" is 0) (3-buo mof enyl)
-Inxazole can be prepared by reacting cyclic t o 2 ty) compounds with hydroxylamine hydrochloride.

Reaction Scheme 35 The reaction of Reaction Scheme 35 is carried out in ethanol at 25° to 80°C for 3 to 16 hours.

The product is isolated by addition of water and extraction with methylene chloride. The product is purified by recrystallization or column chromatography. Starting materials can be prepared by known methods such as V, Hengατtngτ
Other The Journal of Organic Chemistry (J, Org Chem.) 1979, L Sat, 374
8. For compounds of Formula 101cL containing a tff substituent on the inxazole ring, the reaction of Reaction Scheme 36 is similar to H, Yasuda (Dq Gakushu Zasshi, 1959.79°623) and Poplar/Sky (
Bobranski) and Voto7skii (IVo
jtowski)'s Rokczniki Chemistry (Ro
eznikj Chetn, ), 1964.1, 13
It describes a process similar to that described by No. 27.

Reaction Scheme 3'6- Emeritus 1 R1 101α 4-substituted inthiazole U4n of Formula 105 can be produced using the compounds of Formula 102 as a starting material in a manner similar to the method of Reaction Scheme 29. The subsequent conversion to sulfonamides of formula 106 can be carried out by the method of reaction scheme 8.

1-Methylpyrazole-4- of formula 2 and u (tC=O)
il) thiophene MuS, relay 7 ors (Li1j
efora) and 5. p”o know (Gro-
nowitz) tr) Chem, Scr, 1979
, Mu, 102. Each sulfonamide of Formula 108 can be synthesized by the method described in Reaction Scheme 8. When 9 is 1 or Fi2, the formula stands for thiophores and their individual sulfo/amides #A! ' is manufactured in a similar manner.

Reaction Schemes 37 and 38 illustrate the preparation of (2-oxacylyl)thiophores of Formula 109.

Details of their manufacture can be found in W. E. Ca5s, The Journal of the American Chemical Society (J. Δm, Chgm, Soc.), 1942.
, to 4.7ss and “Mgter
cyclic compound)”,
Volume 5, R, C.

Elderfield (EldgrfscLd), Ed
, J.

Willy & Sans°, New York, 19-3
7. There are 5 self-explanations in 5 chapters.

Reaction formula 37 [Shiko 1. R, Fu-Yo and A4 with H] Li and Shikito! The thiophores of U can be converted to the corresponding sulfo/amides of formula 112 by a force G similar to that described in Scheme I3.

The (2-thiazolyl)thiophores above in formula 2 are represented by reaction formula 3.
It can be manufactured using 9 steps.

For details regarding the color-matched synthesis method, please refer to the above-mentioned references. Conversion of Formula 114 to sulfonamides can be carried out using the technique shown in Scheme 13.

116 The (1-methylimidazol-2-yl)thiophenols of the formula Nijotama can be produced by the method shown in Reaction Scheme 40.

A condensation reaction between chenylaldehyde, α-diketo/and excess amine produces an imidazole frame of formula 115. Regarding the theory of such reactions, see 4, 4 of the above cited document.
See 5 and 8 Sui.

The sulfonamides of the finished product can be produced from 115 by the method of Reaction Formula 13.

Schemes 41, 42 and 4312 show synthetic methods that can be used to produce (5-oxacylyl)-thiophenones.

[In the formula, R8 is H] z 11U Reaction formula 43 [In the formula, R3 and R4 are I and b, and details of the reactions described in Reaction formulas 39 and 40 can be found in the above-mentioned cited document. It is written in Chapter 5. Details of steps related to reaction formula 41 m1-1.4, 8'lI, /: Van LextsttL, 13. E, lfoquenboom and tt
, Tetτα-hedron Let of Sevprius (5er-derius)
t,) 1972.2369 Written from K. Compounds of formula 118 can be obtained by a very similar process and subsequent bromination of the appropriate methylene moieties, and details of the bromination can be found in S. Four Chemistry (Ark, Ke
m, ), 1958, supra A1295.

In reaction formula 42f, the α-hydroxyketone ah of formula 119 is obtained from a suitable chenylcarboxylic acid chloride and a suitable 1,1,2-tris[()limethylsilyl)oxycoalkene! L! 4. Wiss-ne'r, J.E., Birnbaum (H.
irnbaum) and Tori, E., Will77 (Wi
lson) Journal of Medical Chemistry (J, Med.

Chem, ), 1980.23.715.

In all cases, the conversion of the compounds above to sulfonamides is carried out according to Scheme 13.

The same liquid (5-thiazolyl)thiophenro of formula 121 is prepared according to the method shown in the reaction formula , Narukami Uni also uses the method of reaction formula 13 to obtain formula 12
Converted to sulfonamides.

(5-imidazolyl)thiophenes with d:123 are prepared according to Reaction Scheme 45.

” The reaction between an appropriate α-haloketone and an amidine on top of each other is R
, ,=H] to produce imidazoles of the formula Rainbow 1]. N-Alkylation of Fi is carried out using general procedures obvious to those skilled in the art to give compounds of formula Uni and 124. The sulfo/amides of Anagami and 126 are produced by fB according to Reaction Scheme 14.

The (4-oxacylyl)thiophenes of formula 127 can be produced by a process similar to that described in scheme 41 or 42, with limited substituents and the production of a sulfonamide, but otherwise the same as scheme 13. The process provides compounds of formula 128.

formula! Another method for synthesizing oxazole r of 27 is reaction formula 45r.
It is shown as 1 in L. It is similar to that shown in F'i reaction formula 41.

Reaction formula 45rL 27a In formula C, BhCl-Cs alkyl, amine] When B-amine is the compound of formula 127b, Sandmeyer type reaction conditions are novel as shown in reaction formula 45b. 2-substituted oxazoles.

1 to 24 hours 1? ! The (4-thiazolyl)thiophenes of the above formula 129 are represented by reaction formula 4.
5 using the thioamide of Scheme 44.

These thiazoles can be prepared by formula 1 using the method of reaction formula 7.
It was used in the sulfo/amide neck of 30-. Similarly, processes using schemes 45α and 45b also provide thiazoles of formula 129.

Compounds of "YU1 YU reciprocal EYU" or "UUU" (0-16, r'=o
) can be prepared by the example steps shown in Reaction Scheme 46.

Above and above ”””− The 1,3-oxazolines of reaction formula 46 are B.

L, Wehrmeistl - (Fehrmeistgr
), The Journal of the Organic Gumistry (J, Org, Cng77!), 1961, 1961, step 382I, processed, carboxylic acid and a suitable amino alcohol in toluene. Heat up Kyoto? Remove B
In particular, he left behind 21. Product oxazoli/
Eyu and L can be lithiated using a loop titer in an ether C medium. SC),'
<The treatment used and the conversion to the compounds of formula Ll are carried out by the steps abbreviated in reaction formula 13 or by reaction formula 4.
As shown in 6, Sulfy/Seishoku is NC3 (N-
Chloro-coding is carried out by oxidizing with <acid imide) and converting 8'II to 8J to amide/8゜q to Q-1s (F is S), q-17 and Q-4.
Intermediate oxazolines that are 1, thiagrin #1
and imirsili/mti, which can be prepared by steps similar to Scheme 46 or by methods known in the art.

Regarding the supplementary 71 law, see the above quotation from R.C. Elderquirt°, R.V.
, Fern and LC, Rigbso*tter Chemical Review x (Chem.

h2), 1954, -■, 543, R, ii, Willie (tViley) and Ri, L,
Benent (HeILsr, et t), Jr.
Chemical Nhi-use (Ch-Usukeji), 194
See 4. Earthworks, 447.

Formula 1340: JIIS Kimonohani (Q-18, Qi is 0) dS, Gronowitz and S, Lilyforus' (
:h6m, Scr, 1 : As shown in reaction formula 47 by the step of 179.13.137, i? !
Can be built.

Scheme 47 According to Scheme 47, bromothiophene is reacted with the sodium salt of pyrazole in pyridine containing a copper catalyst. lithiation of chenylpyrazole and S,
N, Bhattacharya (Bnα11α-charya)
Other The Journal of the Chemica/l, = Nsayetei (J, Chem, Soc,) c, 1968.
1263 by reaction with υsulfuryl chloride to form formula 1
34 compounds can be provided.

For Q-18 where n = 1 or 2,
Suitable thiophenes of Formula 134C are prepared according to Scheme 47a.

The conversion of BF 34C to sulfonamides is carried out in the same manner as shown in Reaction Scheme 13.

In a similar manner, formula L1dan or upper main construction earth [(2-19)
The compounds can be produced by the steps shown in Reaction Schemes 48 and 49.

Equation 48 Equation 49 Core 36b This reaction is carried out in the presence of a suitable solvent such as dimethylformamide, N-methylpyrolide 7, T17F or pyridine at room temperature to reflux temperature for 1 to 24 hours.

Reaction Scheme 50 shows the synthesis of thiophenes containing Q-20.

When the chloride of Uni-Li-Arigari Nijishiki L1 reacts with hydrazino,
will produce the above hydrazide. USA%l￥
According to ls O8, 223, 139 is 1000-150
It will react with the diorthoester at 0.degree. C. for 5 to 24 hours to form oxadiazoles of formula 140. Deprotection of the sulfo/amide moiety using a strong acid such as trifluoroacetic acid yields the desired sulfonamides. Synthesis of starting thiophenes of "Ana Retired Emperor" is European! It can be carried out by the method taught in patent application 30.142.

Reaction formula 5OaFiR, is SR,! It shows the production of thiophenes of formula L1UA.

Reaction formula 50α IchiriA [In the formula, R1'! = ' I -C4 alkyl, C5-C, alkenyl, C, -C4 alkynyl, C, -C, cyanoalkyl, carbonylmethyl, ethoxycarbonylmethyl, methylcarbonylmethyl or halogen] Reaction of reaction formula 50α &-tE , Hoggar
t5's The Journal of the Chemical Society (J,C5em,soc,), 4811 (195
It is carried out according to the same steps as described in 2>. That is, the hydrazide is reacted with carbon disulfide in ethanol at reflux in the presence of a base such as potassium hydroxide for 4 to 16 hours, drained and acidified with hydrochloric acid to form compound 140a. Then compound 140α
is reacted with R1,I in the presence of base in ethanol to give compound 137a.

Formula earthwork compounds (Q-21, F'=0) are shown in reaction formula 5.
As shown in 1 (P, Dupus [(htblLs
l, B, Decroiz, J
, s-A, Moreland and p.
Ann, Chim
, (paris)), 1975, 4-2L4
tlo, page 331, page 1.

Reaction formula 51 Compound L is reacted with excess orthoformate over 100'-150°C f1 to 24 hours to form 141(R2'
=H) is given. Her is NC5-4 or NB respectively
c t by selective deprotonation and disappearance with S
You can also exchange it for -4 or Br.

Regarding x7 = cg, the compound Nisotyu is US patented:
Acetyl chloride and B according to I, 27 Q, 029
Reacts with F, ・Et, and O.

Similarly, 1.3.4-thiadiazole-5- of Anagami Toyu
Ilthiophene Fic, Einsw
orth) and R,(:,, Jones
s)'s The Journal Off the American Chemikatshi Sozuyetei (724m, Chtm Seiji Ni),
1955, Eyu, 621 Namibini H, Wa 1 Di/Kuru (W
'eidinger) O and J, Franz (K?''
anz)'s Herichte der Doinochen Hemin/
(Be2), 196396.1
It can be manufactured according to the technique described by No. 019.

1 Soil and reaction formula 52 are 1.2.4-thiadiazole- of formula 144
The production of 3-ylthiophenes is shown.

Reaction formula 52 The reaction of reaction formula 52 is J,y Rubler (Goerde-1
eτ) and M, Budnowski (Bxdnowski
), M Hemituzoyu Berichte (Chetn, Be de J
, 196 L, 94.1682. That is, an amidine of formula 145, obtained via the corresponding carboxylic acid salt, is mixed with chloromethylsulfenyl chloride and water η in a solvent such as 1,4-dioxane over a period of 02 to 11 hours at a temperature of about 0°C. ;: Preparation of thiophene of formula 146 by processing sodium chloride -j 9. The protecting group is removed using a strong chemical to give the sulfonamide of formula 1.

), S:y (Li'n), S, A, Land' (La
nd), M.

F, o Lovell and A', A
, Perkinso?L's The Journal of Organic Chemistry (J,O
r, C) Lem, ), 1979, 4160 is 1.2.4-
1 shows a method for producing oxadiazol-5-yl-thiophenes.

Reaction formula 53 Formula 14 obtained by amination of the corresponding carboxylate salt
The amide of 9 is reacted with an alkali/amide dimethyl acetal of 100% at 80 DEG to 120 DEG C. for 0.3 to 3 hours to produce compounds of formula 150. These compounds? dissolved in aqueous 1,4-dioxane-acetic acid and at fM degrees ranging between 25° and 90°C.
．． It can be reacted with hydroxy/ruami/ for 5 to 3 hours to produce ``shikiritama'' xadiazole, which can be converted into -
(or perhaps simultaneously) the protecting group is removed using a strong acid to give the formal sulfonamide.

In exactly the same manner, using conditions similar to those described by Scheme 53, l,2°4-thiadiazol-5-ylthiophenes of formula 152 can be prepared; , Lang's The Journal Off the Organic Chemistry (4 years old),
See 1980, Dotate, 3750.

1,2,4-thiazol-4-ylthiophenes of formula 153 are described in U.S. Pat.
ri)'s The Journal Off De Chemical So 1
Yeti (/,, 4m, Chcrn, Soc, )
, I can follow the teachings of A3359. , anti-LC equation 54 shows this process.

Reaction formula 54 The ketone of formula 154 reacts with ethyl rubazate, resulting in the disappearance of the 6-hydrane F, and its reaction with theonyl monochloride also leads to the formation of y-'y15:). Raw D
4.

Formula 15 By fulfilling restrictive conditions and removing these groups, the sulfonamide dry group I of formula 153 is obtained.
1,2,5-thiadiazol-3-ylthio7ine of 6; Thiophene of formula 31; tinstock), P. Davis (D.
ajJis), B, C: yf le y, M: y (llan
delsman) and R.

Tsuru (Twit)'s Journal Off Orcanitz 32
．． 2823iV, Berthier (Ber,!inin 2 and P, Hino (ptno) Anghe
International 'Le Eddy'/Yon Ink Cliff'/Yu (Angew, Chem, Int,
Ed, En 1. ) 1966.5.514 line vc
s, r taka (, Iftx t ska), A, honki (Hosoki), K, takahan (Tan α ru ashi)
) and Af, Tashino ("I'ashino"), Synthesis 1979.524.

Methyl-1,5,4-triazol-2-ylthiophene compound 1 of Formula 137 can be prepared by the method shown in Reaction Scheme 55.

Reaction Scheme 55 N-aminoamides of formula 158 are combined with incyanates and anti-J6L under reflux, for example in acetone or 2-getanone, ua=g*A, to give appendages of formula 158cL. When these are heated, they turn into silica, and at the same time, water is expelled, formula 15
9 triacylones are produced. Treatment with phosphorus trinomide and phosphorus oxy7chloride under reflux gives the 2-chloro-
Triazoles are given, and the 7″L is for example/) M I
In a different aprotic bath medium such as ')
; treatment with JIt produces a substituted sulfonamide of formula 137. Compounds of formula 158 are of formula 161
It is synthesized by treating esters of with hydrazines.

Methyl-1,2,4-)lyazol-5-ylthiophenes of Formula 162 can be synthesized by the steps shown in Reaction Scheme 56.

Y, sy (L<-n), 5. ．． 4. Run r (L(
LnQ'), M, F, o-yl (LoveL)
and N, A, Parkinson CPSrkins.
on) The Journal of Organic Chemistry (J, Org.

C5gm, ), 197? , 44.460 shows that reaction of compounds of formula 150 with furkylhydrazines over CL5~'2 hours at temperatures between 50'' and 90°C in acetic acid will give triazoles of formula 163. Removal of protecting groups to produce sulfonamides of formula 162 can be carried out during the analyte or can be subsequently removed by the use of strong acids.

Furthermore, compounds of formula 162 can be prepared in a manner similar to that of scheme 55 using the appropriate cyanate or thiocyanate, with the necessary intermediate relative formula 158
gives the compounds of b.

R;=/<, formula 164-methyl-1,2.

4-)S7zol-3-ylthiophene>, II l'
AI shown in Lt skin response formula 37, Atkinson and! , Polya
The Journal of the Chemical Society (J.C., S.O.C.), 1954
, 3319.

Reaction Scheme 37 A hydrazine of Formula 163 is reacted with an anhydride at a temperature in the range of 25" to 100°C for about 0.5 to 2 hours to produce triazoles of Formula 166. Removal provides the sulfonamide at of formula 164. Hydrazine 163 can be prepared by reaction of nitrile 161 with alkylhydrazines.

Similar treatment of Formula 163 with diphenyl carbonate or phosgene produces triacylones of Formula 166α shown in Scheme 37α. Conversion of Formula 164b to sulfonamides is carried out in a manner similar to Reaction Scheme 37.

Reaction formula 37α 66a 1.2.4-) Reazolylthiophenes of formula 167 can be synthesized according to the formation of reaction formula 58 (introduction).

Reaction formula 58% Formula % Formula 17
H'AL can be obtained from the triazoles of formula 168 by the reaction of 1-molymer-7ene of formula 168 and 1.2.4-) rearylna) of formula 169. Alternatively, 170 can be subjected to an oxidizing step, with intermediate sulfonyl chloride keamination to produce sulfonamides of formula 167.

On the other hand, sulfonamides of Formula 167 where R4=H can be produced by the steps shown in Reaction Scheme 58a.

Reaction formula 58α 5-7゛a mochi:t7enkNKl)jfF in fm(l
1, 2, 4-) of formula 169 using a catalyst! Coupling with sodium salt of J azole. Next, the generated biaryl of formula 170α was selectively lithiated at position 14 using n-glylithium in diethyl ether at -100°C, and the electrophilic substance R2'Xt-
The biaryls of formula 1706 are produced by using and vanishing. 170b is sulfonamidated in a manner similar to that described in Scheme 12 to give the desired 167.

n is 1 or 2, add the appropriate triazole sodium salt to the aldehyde of formula 170c,
It can be converted to sulfonamides of formula 167α by the method of reaction scheme 5Bb.

Reaction formula 5Bb 70d 70e 167α C, Einsworth, etc.
1-formyl-2-(3'-promotininyl) of formula 172 as shown in Scheme 59 below according to the steps described by Σ 353,
Compounds of formula 171 can be prepared by reacting hydrazine with excess formamide under reflux for about 1 to 6 hours.

Reaction formula 59 On the other hand, compounds of formula 171 are converted from 2,5-dibromothiophene to 1 of formula 169 as shown in reaction formula 60.
．． 2.4-) By reaction with the sodium salt of lyazole, υ
Can be manufactured.

This reaction can be carried out by the steps described in Equations 47, 48 and 49.

The compound mu of formula 171 is M, Kahn and/or rl! IJA (potycL)'s The Journal of the Chemical Industry (J.

It can also be prepared by a modified Ullmann reaction according to the teachings of Chgm, Soc, N. C0, 1970, 83.

Formula 167d (Q-29) (D compounds are reaction formula 61
It can be manufactured by the process shown in the figure.

Reaction Scheme 61 2-Amino-5-thiophene-t-butylsulfonamide 59, prepared by the process of Equation 23, was reacted at 150° according to methods known in the art, e.g., in C. Eisworth et al., cited above. Treat with N,N'-diacylhydrazine at ~200<0>C for α5~2 hours. Formula 16
The 1,3°4-triazol-3-yl-thiophenes of 7b are prepared as shown in Scheme 62.

The aminothiophene of formula 172 is
C) over a period of about 0.5 to 2 hours to form triazoles of formula 175. Conversion of these triazoles to sulfonamides of Formula 167b can be carried out as shown in Schemes 58 and 61.

LL main 173 ・ 67b n7'+: 1 place in the station building with 14 or 2, formula 167e
The sulfonamides of I! Reaction formula bi to create +1
A completely similar process to b can be used for the 5-viridine T, J of formulas 174, 175 and 176.
, Van Bttrgen
The Journal of Organic Chemistry (J.

Org, Chgm, ), 1969.34.3175. In the case of 177, the sulfonamides of this formula can be prepared by the process of reaction scheme 7, and the formula 178
And for the sulfonamides of 179, reaction formula 14
The following method will probably preserve 'A' better.

two! ---Two? ! −12ξl V=5rノ,ノV
d.

When n'=1, the corresponding pyridinylthiophene sulfonamide 4A'J! It can be produced by treating with 74-chlorobenzene in ll-chloroform. The produced molecules precipitate from the bath liquid into each station.

When n is 1 or 2, formulas 177-179 Not?
r gives the desired sulfonamides.

5-pyrimidin-2-ylthiophenes of formula 1 BS
-Gronowitz and S.
, manufactured according to the Lilyefors Acta technique and its modifications. Sulfonamides of formula 181 can be prepared by the method of reaction formula 14 (
/C.

One type of F=H 181V=502NH.

3-pyrimidin-4-ylthiophenes of formula 182 are R
, E, van der Stoehl (Vandgr 5t
ool) and H,C,777-del glass (V
and dgr piα8)'s The Journal Otsu.
The Chemical Society A-kin 1 (J, C to g
m, soc,, pgrkin +), 197 yu, 2
59B. Conversion of Formula 183 to sulfonamides is accomplished according to Scheme 140 synthetic sequence.

182 〆=H'+ 83 V=SQ, j~'H7' 5- of formula 184
Pyrimidin-5-ylthiophenes are derived from Chtm, Scr, 1 of S. Gronowitz and S6 Reiphorus.
97 B, 13.5? and the use of the synthetic methods described in The Organic Chemist 177JE and their variations. ,F
The right structure of concentric sulfo/amides of formula 183 is according to the method of reaction formula 14! l) Na stone.

184 4’=# 3-pyrazinylthio7275 of formula 18B is J.

Gluginone (BowrgusgnorL), LM, Bowchy (CBouchy), 1. C, Clinet [(
Lintt) and G, Qugginer.
r) congras rendus hegdomadaires de ciance de u academie de cayens, 2
81.1019 method. The synthesis of the sulfonamide of Formula 187 can be carried out using the steps described in Scheme 14.

3-pyridazin-5-ylthiafenes of formula 188 are J
, Purginone, C, Be]-CEtcat). Conversion of formula 189 to sulfonamides is carried out by the method of reaction scheme 14.

187 V=502Nll, j 89
V=SO, N8 Formula 190 3- (1, '3.5-
triazin-2-yl) thiophene/呵! ('J J
, A, Naya Ta'Labartei (Ci+, akrab
arti), R, l? ”, Gulde/rng (G
ov, lding) and L) 7do (Todd)'s The Journal Og Su' Chemical Saupeille, 1?7
3.2499 people can move 1 ζtυ pieces.

Combined i+V, Jl, k-Confucian 1, 1,3,5-trianone G, smolin (Si+, otjtt3, f,
, qf, z-, ); 0. UHr4-to ()<apv
npo・rt, ), L, ()
'1'he Chemi-stryof
Nojgteroclic Com,ponnds
@, Volume 15, Willy Intersigns, New York.
j corresponding sulponamides (-[Scheme 192 produced by the chemical method G.1 described in Reaction Scheme 14)
5-(1,2,4-triazin-5-yl)thiophene 3 can be prepared by a similar heterogeneous method to the preparation of thiophenes of formula 190.

Rybovsky (Rybotn8) and g, c,
Van der Plas' The Journal of Organic Chemistry (J, Org, am in C),
It can be obtained by the method of 1980.45.881.

In addition, the sulfonamide of formula 193 can be obtained by using 1r of the bottom step described in reaction formula 14.

191 F”=SO, Nil, 193
V=SO, NH.

The 3-(1,2,5-naazisol-5-yl)booth-phenes of formula 195 are described by the anti-2 formula
The thiophene ζ4f7'J6 of formula 196 is produced by the 17th modification of the synthesis method of 55. These thioenes can be manually determined from 2 (the corresponding ketone).

1?5 Q is Q-35, q-54, Q-35, q-37 (J -
38, q-39, (,140, Q'4.5 o: and Q-4
Chemical formula 8 of formula 2, which is 4, IPJ≦ is abbreviated to Reaction Formulas B and 9, and according to the reaction in which t is 1t, and h is the order, ・l・blue t is obtained.

The formula 5 libilimin... and the triglyceride steel are the intermediate products required for the production of the compounds of the formulas α, rbP and Ic of the present invention. The combination of such pyrimidines and trianes is necessary or can be prepared by methods obvious to those skilled in the art.

The 2- and 3-pyridine sulfonates of the above formula 197a are the necessary intermediates for the preparation of the 11 compounds which have been persistently unknown, and can be prepared by methods known from the literature or by modifications thereof. It can be installed by experts in this technology.

For example, pyrazol-1-yl at the 2-position, 1.2.4
-) Riazol-1-yl or imidazol-1-yl/
l-group (Q to Q-52, Q-b1t721gQ-66)-(iL, l-pleasantness I'5:S, 197
a) 3-Birinsulfonamide is expressed in reaction formula 6 below.
3 shows the anti-Lr, -i・:λ presser 9j,
I can't wait.

Anti-Otsu-shiki 63 and η辷ヱmutan C parishioner, E-yu Arashi piJ vko;-3 knowledge-;Sartei 4>:, U <deoku QIrJL, /-52, Q-6
1 or r; 1-66, and n is 0.1 or 2] Reaction 63(a) In this reaction, 3-nitropyridines 198 are reacted with stannous chloride by conventional methods, e.g. in hydrochloric acid. is reduced to the corresponding 3-aminopyridine by the reaction. A detailed description and reference description of this and other methods for the reduction of nitropyridines to the corresponding aminopyridines can be found in '? ,! The C
remistry ofHeterocyclic C
ompolLnds)”, series, A.

Weissberger, E
d, Pyridine and Derivatives 1, Chapter ■, pp. 8-10, E. Klingsberg
erg).

Ed, written inside. 3-Nitropyridines 198
Suitable 2-chloro-3-nitroviridines are US Pat.
&489,761 by reaction with the sodium salts of appropriate pyrazoles, 1,2,4-)lyazoles or imidazoles in an inert solvent, e.g. N,N-dimethylformamide (DMF). .

Reaction 63(b) In this reaction, 3-pyridinesulfonyl chloride p20
0 was obtained by diazotizing the corresponding 3-aminopyridine M with salt I, N and sodium nitrite in vinegar and diazotizing the diazonium salt with either steel chloride (1) or copper chloride (If) in acetic acid. By reacting with excess sulfur dioxide in the presence of! A will be built. The details relate to Reaction Formula 63(6). See reactions similar to those described in the references cited above.

5-, thioxazole- at the 3- and 2-positions, respectively.
2- and 3-pyridine sulfonamides substituted with a 2-yl group and having formula 197α (Q is Q-53) can be prepared from the corresponding 2- and 3-mercaptopyridylcarboxylic acids 2o1 in the following reaction scheme 64. It can be produced by the reaction sequence shown in b.

Reaction formula 64 % Formula % [where El is as defined above, Rj/ is C, -C, alkyl, CCH=CEt or CF, H, and ↓f is C1, Dr is still I] Reaction 64 (α) These reactions (Pyridine sulfonamide! A$
It Y, Morisawa et al. Journal of Medical Chemistry (2nd Engineering I)
fed, Chem, ), 23.1376 (1
980). This method consists of (1) chlorinating appropriate 2-carboxy-3-mercaptopyrimidines or 3-carboxy-2-mercaptopyridines in 'tQ hydrochloric acid and water at about -25 to 5°C to obtain the corresponding carboxyl compound; (ii) amination of the sulfonyl chloride with ammonium hydroxide to produce the corresponding carboxy/pyridyl sulfonamides; and (iii) these compounds. sulfur G in methanol
餉Q! The sulfonamides 202 are produced by esterification by refluxing them together.

Alternatively, mercaptopyridine Q201 can be chlorinated in the presence of potassium difluoride in an inert solvent such as water and methanol at about -30°C to 0°C to produce the corresponding carboxypyridylsulfonyl fluoride sequence. Subsequent reaction of these compounds with ammonia can give the corresponding sulfonamides. Further details Kll F-1D, J, Brown (BTO
wTL) Ruled and S.

A. Hoski'rLs' The Journal A/-Off the Chemical Society Perkin.
Trans I (J, Chetn, Soc, Pe
rkin Trans'), 522 (1972).

Reaction 64(b) This reaction is also carried out analogously to the teachings of the references cited above. This method involves preparing the pyridyl esters 202 in methanol under reflux for 5 to 6 hours to prepare a hydrazine-containing compound.
It consists of reacting with water salt. Under certain conditions, sulfonamides 202 can be ring-closed into saccharin-like structures during their preparation in reaction 64(α) or during reflux with hydrazine in reaction 64(b). .

In either case, subsequent reaction with hydrazine as described above can provide the hydrazide.

Reaction 64(c) Conversion of hydrazides to 5-mercapto-oxadiazole domains is described in the literature, e.g. R, F., Young.
and II, Food, The Journal of the Chemical Society (J, Am,
'Ch, em, Soc, ), 77.4'OO(1
955). In a typical process, hydrazide i203 is added in equimolar amounts? Heat in a methanol or ethanol solvent with potassium hydroxide and an excess of carbon disulfide until hydrogen sulfide evolution has nearly ceased. Concentrate the solution, add water to the residue, filter the aqueous suspension to remove insoluble impurities, and add water to the residue.
Liquid with hydrochloric acid? The oxadiazole Q197d (R≦′=7L) is separated by sexualization and filtration.

Alkylation of 5-mercabutoxadiazolec is also reported in the literature.
, r) iol, Chem, ), < o, 17
(1976). Typically, oxadiazoles 197d (R;=H) are dissolved in an inert solvent such as methanol or ethanol under reflux for 0.5-2.
React for 4 hours with equimolar amounts of a base 2, such as potassium hydroxide, and an estimated 9 alkylating agents R"M. 197 dF'i of sulfonamides,
It is isolated by addition of water to the residue and filtration.

When R;=CF, Fl, the reaction is preferably D
, 60° C. in WF stone soot at 0° C. using potassium anthracite with excess O as the base. After addition of water, sulfonamides 197d are isolated by filtration.

The 2- and 3-pyridine sulfonamides of formula 197a, in which the 7-enyl group is placed at 3- and 2-, respectively, are the corresponding 3-phenyl-2-pyridinol: 5 and 2-phenyl-3-pyridinol, It can be produced from around 20 steps according to the reaction sequence shown in the following equation 63.

Reaction 2 63 204 and 11 (
b) [where El is as defined above] Reaction 63 (α) In these reactions, mercaptopyridines 205 are prepared by B, Blank et al. , 11ed, Chem.
), L], 1063 (1974). This method (i) converts the viridinols 204 into D! Reaction with dimethylthiocarbamoyl chloride and a base such as 1,4-diaza-piacroCZZ2]octane (D, IDC0) in VF to produce the corresponding N,A'-dimethyl-〇-thiocarbamates. (ii) For example, one of these compounds O
! -21 species heated to high temperatures such as °C to form the corresponding N,N-dimethyl-5-carbamates; and <1ii
) heating these compounds with a base such as sodium carbonate or sodium hydroxide in an inert solvent such as methanol to form mercaptopyridines 205;

Reaction 63(6) These reactions are carried out by steps similar to those described above for the production of 202 (reaction formula 64α).

2- and 3-pyridine sulfonamides of formula 197α (Q is Q-72 to Q-81) F′ It can be produced by the reaction sequence shown in Reaction Scheme 66 below.

Reaction formula 66 (α) I37 (b) Ki' Phantom rho (c) [1 in the formula. E is H or CH, dechiri, and Q is Q
-72 to Q-81] Compounds of formula: 197f are European Patent Application No. 83
, 476 (published December 13, 1983).

Reaction 66 (α,b) A suitable 2-promo 3=(N-t-butyl)pyridine sulfonamide or 3-promo 2-(N-1-butyl)pyridine sulfonamide is added to an ethereal compound such as tetrahydrofuran. Dissolve in solvent and add 2 elements of n-butyllithium in hexane at about -70°C. −
After 1-5 hours at 70°C, the corresponding compound of formula 207 is formed. 1 eyelid iodized steel (1) at about -70℃
and then a 1-1.5 equiangular appropriately substituted heteroaromatic iodide of formula 208 is added. Reaction mixture to 0
Stir at −70° C. for 1-3 days, concentrate, and pour onto aqueous ammonia. Compounds of formula 209 are brought to a single pH by filtration or, if an oil, by extraction with methylene chloride and concentration. Compounds 209 can be further purified by recrystallization or chromatographic steps. Compounds of formulas 206 and 208 can be prepared by methods known to those skilled in the art. Preparation of compounds of formula 208 Appropriate references are found in European Patent Application No. 8 S, 476.

Reaction 66(C) This reaction consists of compound of formula 209 with 2-10 equivalents of trifluoroacetic acid or aqueous HBr with or without inert gQ at 30'-70°C for 1-3 hours II) t2 It is carried out by stirring. The product tctrf is trifluorovinegar Q store or hydrogen bromide 5
) as a salt, 'tX and can be isolated by evaporation of excess acid and trituration with ether. By neutralizing the salt with aqueous base, extracting in an organic solvent, and concentrating the organic extract; rr% i', (i base is obtained.

The 2- and 3-pyridine sulfonamides of formula 197g can be prepared in one step as shown in Scheme 67 in a manner similar to the preparation of compound fA197d shown in Scheme 64.

Reaction Scheme 67 [where El is as defined above and R41 is C,
-C3 alkyl or CF, H″t′, and f is ct, nγ is still I] Formula 197h in Scheme 68a is written for the preparation of similar compounds in Scheme 6G. The lithium salt 207α can be prepared from the lithium salt 207α by the following steps, and compound 197C can be prepared η as shown in Scheme 68b.

Reaction formula 68α [In the formula, R3 is H, and Q is Q-72 to Q-81] Reaction formula s8b Dilithio salt 207a is R, E, sumi/1. (5mi
th,).

Journal of Organic Chemistry (J, Org, C) tem, by S, Sr-Boatman and C, R, Bauser, );
33.2083 (1968) by lithiation of appropriate picoline sulfonamides.

Nitropyridines of formula 197j containing o-furkylfuran or thiophene groups (Q is Q-67 to Q-7
0) can be prepared by formula 6 in analogy to the teachings of European Patent Application No. 83.476 and the references cited therein.
It can be manufactured as shown in 9.

Reaction 269 "where EI and n are as originally defined and Q is Q-67 to Q-71" That is, a furyl- or chenyl copper compound of formula 222 is reacted with e.g. pyridine or Inert 7S like quinoline
O all over the prefecture! React with 0-(iodoalkyl)nitropyridine of formula 221 for 1-3 hours at -60°C. extraction,
The corresponding lithium compounds of formula 222 can be prepared by stripping the corresponding lithium compounds in an inert solution such as ethyl ether and by chromatographic treatment of the crude product. Models are formed by reacting the compounds with cuprous iodide or cuprous bromide. Detailed procedures for similar types of reactions are described in the following bibliography: (Ni
lgson) and C6 Ullenius (Ulleni-L
Ls), Acta Hemi-Riki Scande Inavika <Act
Cm in a and c.

5CQ, nd, l, 24, 2379 -2388
(+970) ;C, Urenius, Acta, Hemi force, Scandinavian force (Acta, Chem, 5Cand,)
,” 3383-3386 (1972).

2- and 3-pyridine sulfonamides of formula 197a substituted with i)-71 at the 3- and 2-positions, respectively, can be prepared as shown in Scheme 70.

Reaction formula 70 [wherein E is H or C1l, and n is 0 or ql
] Formula 197α compound is European 1″y patent application number E
No. 15,476 (published August 10, 1983).

Reaction 70 (α) In this reaction, the dilithio salt 207 or 207a is treated with 300 parts in tetrahydrofuran at -70°C to -80°C. After stirring for 1-3 days at about 25° C., the reaction is quenched by the addition of hydrogen, such as acetic acid, to 210, which is a raw FJ compound, simply “tl,”
and purification by 1.0 stripping and chromatography of the residue.

The reaction with anti-70(b) is carried out by a process similar to that described in Scheme 66(c).

3-biwadine sulfone amitoco of formula 197 (
(Q is Q-67 to Q-70) can be produced as shown in Reaction Scheme 71 below.

Reaction formula 71 In formula C, E, ,R,! , R4 and R34 are as originally defined, Q is Q-67 to Q-70, and W is 0 or S
Reaction Scheme 71(α,b) In Reaction 71(α), a furyl- or chenyl copper compound of formula 212 is reacted with a suitable compound of Rolow or bromonitropyridine in a solvent such as pyridine or quinoline. Let me go home. Copper compounds with Te'< 212 are compatible.
The lithium compounds of 4-4 are prepared by reacting them with cupric iodide or cupric tetrachloride, such as diethyl ether, in a 7-metre sieve. Detailed steps for Ne-type reactions are described in the following references: Acta hemicarscandeinavi force (Acta, Ch, em, 5, lf, Nirnon and C, Urenius)
cand, ), 24.2379-2388 (1970>
;C, Acta Hemiforce Scandinavica of Urenius (/fcta, Chem, Sr:a?ld,),
26.3383-3386 (Formula 1 substituted with furan or thiophene group at 19723°3-position)
97/2-pyridine sulfonamides (Q is Q-67
~Q-70) can be produced according to the reaction sequence shown in Reaction Formula 72 below.

Reaction formula 72% Formula % [In the formula, EI % R1! , R4 and EI4 are as originally defined, where FicEpH, CM, -4 or CM, C, H, delari, Q is Q-67 to Q-70, and W is O or S] Reaction 72 (α) In this reaction, d,2-halo-3-pyridyldiazonium is converted into 11-1' in the presence of an F compound such as ferric chloride.
c Coupling with n-substituted thiophene or furan. This 5. , the answer is om-berg (niom-berg)
) and buffer :/ (na r jr, ma ?
The Journal of the American Chemical Industry (J, ylm, (:l;, et
n, Soc, ), 46.2339 (+924)
; J, Johnson (Job, n5on) The Journal of Chemical Research (J, Chsm)
, SoC, ), 895 (1946) and The Journal of Pharmaco-Eutica A, or simple variations thereof. For complementations in which both the α- and β-positions of the thiophene or furano are available for coupling, two-doku true forms are commonly obtained, with the α-coupled product being the predominant isomer. These isomers can be isolated by fractional crystallization or chromatography steps. can.

Reaction 72(b) This reaction results in a thiobilinone 21f′i − of formula 216,
For example, D
It is prepared by treatment with potassium pennol or decopyl mercagutide at about 25° to 150° C. for 1 to 24 hours in an inert solvent such as MF. After isolation by the general method, the product 216 is obtained by a chromatographic step! Can be made by ft.

Reaction 72(C) In this reaction, the products of Reaction 72(b) are oxidatively chlorinated in the presence of water in a suitable inert solvent such as chloroform, methylene chloride or acetic acid to give the corresponding sulfonyl chlorides. Manufacture. The reaction is carried out in the presence of at least 2.5 molar equivalents of water and at least 3 molar equivalents of chlorine.
It is carried out for 1-5 hours at 30@-5.degree.

After separation, the sulfonyl chloride is reacted with ammonium hydroxide over ammonia in a conventional manner.

As shown in Reaction Scheme 73 below, suitable 3-heterocyclic-2-thiopyridine a and 2-
t4-(・,IY!-i′X,-5-chi,? e”)
'/nj'r fik-forming salt-! Formula 197 can also be obtained by conversion to the corresponding sulfonyl chloride fJ] followed by amination to the corresponding sulfonamides.
Other 2- and 6-pyridine sulfonamides of α can be prepared.

Equation 75 [where El is as initially determined and is Rm, C, II, or C1i, C,11] The reaction of Equation 73 is shown in Equation 72(c). Medium and 20
2 (carried out by a method analogous to that described in reaction scheme 5αIK. Compounds of formula 217 are described by those skilled in the art as i) l'e, substituted aromatic heterocycles. Selected from well-known literature processes related to manufacturing. can be produced by applying appropriate methods. The inserted 0-(replaced with 1) nitromurazene to-# is replaced by a bare ring group Q-46~Q
European Patent Application No. 83.975 (published July 20, 1983) describing a process for converting the corresponding O-(heterocyclic)-nitrobenzenes to -66
See, for example, and the references cited therein. By carrying out similar reactions or simple modifications thereof on appropriately substituted nons, one skilled in the art can prepare many of the compounds of formula 217 above.

There are a variety of known methods for adding mercapto or alkylthio groups to the 2- or Fi3-position of the pyrizone ring, which methods can be used to prepare compounds of general formula 217 as depicted in Scheme 73 above. used for. The choice of method used will depend in part on the reaction sequence used to prepare compound 217, as will be obvious to those skilled in the art. These methods include (1) reacting a 3-pyrisorsoazonium salt with potassium ethylxanthate to produce the corresponding 6-mercabutobirinones;
is alkylated to give 3-bentrue or 1-t3-propylthiopyridines by an obvious method; details can be found in Yarnal Off Pharma/I (1967M 29.281 (19741) and See similar reactions described in Off Organic Chemistry 8); (ii) A', V-tumethyl-5-rubamates prepared from 2-also l-13-bilisonols. The corresponding 2-also 1-
t3-mercaptopyrinones; see Scheme 6(α) above for general details: (lIi
) 3-halopyridines containing an active ortho group such as an aldehyde, ketone, carboxylic ester, amide, nitrile or nitro group, for example l) l
The corresponding 3-benzylthiol, also j-t 5-deronozonethiolpyrinone, can be prepared by reacting with potassium zolo/P-thiol or pentylthiol in an inert solvent such as SIF or hexamethylphosphoramide by known methods. Ov) The 2-halogen on the pyrinone ring can be converted to a sulfur nucleophile, such as potassium bisulfide, sodium chloride, 1,000 urea or potassium bennorthiol (hadero 67 thiol). Flfr! ! , to produce 2-thio-substituted bilinones; for details see J. Htt, Chtm, 1, 3.27 (196).
6); 17.149 (19801: 5.647 (1)
9581: The American Chemical Society (J, Am.

Chtm, Soc, ), 68.342 (194
61 and 70.5 qoB <19481; and the 2-aminopyridines were soazotized and converted to 2-viridinol 5, and 1,7"L was converted to 2 using p4s4. - Pyrinonethiols can be converted to VC; details (see Farytαc).

Ed, 5ciX 22, 1069 (19671).

+4.3 of birinone thiol ;', keke°→car'・
The Chemistry of Heterocyclics
rocycLic Cornpoun-ij l”,
SIJ-: fA, Weiss Ircar (lE'tirr)
-htrltr l EcL,,Interscience・
“Pyridine and its derivatives”, part of Publications, New York and London, Part 4, Part 19.
64, H, L, Hale (also written in Hcltl).

Heterocyclic amines of the formula 5 are also important intermediates for the preparation of the compounds of the invention and can be prepared by the person skilled in the art by methods known from the literature or simple variations thereof. For details, the author describes and describes the synthesis of pyridine- and durianonamines substituted with acetals and thioacetals such as, for example, soalkoxymethyl or ld 1 ,3-dioxolan-2-yl. Patent Application No. 84.22a (1983
July 27822 and F, Preker (BrcLkgr
) other f ・') Yarn off the American
Chemical Society 1-T (/, Am, Cktrn
, Sac, ), 69.3072 (19471 Kingyoteru. Also, for example) Loalkoxy/or haloalkylthio group, such as OCH, CH, F, OCH, CF,
See also South African Patent Application No. 825.045 and 825.671 which describes the synthesis of amine pyridines and tri7nones substituted with groups such as , OCF, II or SCF, H. South African Patent Application No. 837.454 (published 5 October 983) describes cycloprobylpyrimisones substituted with groups such as, for example, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylamino, soalkylamino or alfukidialkyl. The synthesis method of trianones and trianones is described.

In addition, 5.6-no and DorofuroC2,5-d] virimisonone 2-amines, cyclobank[d] virimisonone 2-
Amines (5, AmA-21 and 6,7-dihydro-5H-pyranoC2,5-d)pyrimison-2-amines (■, A = A-51 is European Patent Application No. 15,683A It can be manufactured as described in .

In addition, 70(2,3-d]pyrimidine-2-amines (
■, AmA-411″i MiRotsuno patented μ number 4
6.677 b.

Compounds of formula 5, where A is A-5, are described in European Patent Publication No. 73.562. The compound angle of formula 5 where A is A-6 is European Patent Application No. 94,260
It is written inside.

In addition, general methods for the preparation of amine pyridines and trianones are also described in the following literature: The Chemistry of Heterocyclics, Core, Part 7
f Hgttr.

Cyclic CornpoLLndr)” 7 Leeds, published by Interscience Noseprischers Incorporated, New York and London:
・“Pyrimisons”, Volume 16 of the same series, D, J.

Written by Brown (Bτ0W); ・6! - Trianone ρ and derivatives f, ¥4, 13 volumes of the same series, E, Af, Sumo IJ 7 (5rno
lin) Oj O:L, U・5po) (Rtpp
aport) H; and U.S. Pat.
7 (HtLffmats l and F. C. Schaefer's The Journal off O is Nick 12 (1
Commercially suitable fillers of the 9631°2α-techs compounds can be prepared by a number of methods known in the art. For example, some such methods include (1) substances Iα-IeV;
Metal and quaternary ammonium compounds prepared by treatment of compounds of formula 1α-It with solutions of metal or ammonium hydroxides, alkoxides or carbonates which are sufficiently basic with respect to C; For example +
II. Cation exchange by treating the K-yoshi-prepared platform with an aqueous solution of a second cation, especially one whose salts are rather poorly soluble and thus precipitate from solution; (3) Cation exchange of groups containing the cations to be exchanged 9 (cation exchange via fats, especially ■ α-■- and conversion using cations whose salts are water-soluble, and 14) For example, acid addition salts prepared by treatment of compounds of the formula α-■- with suitable strong acids such as trichloroacetic acid rR or i''tP-)luenesulfonic acid are included.

The compounds described in this invention are further illustrated by Examples 1 to 11 below.

Example 1 5-(3-chenyl l-4,5-sohydro 5-100
F thiophene-3-carboxaldehyde, 100m
A water-cooled mixture of 50% aqueous NαOH was added to a water-cooled mixture of methanol, 80% water and 80% aqueous NaOH (approximately 40 mEL). The methanol was removed by rotary evaporation and the mixture was extracted with ether. The ether extract was washed with brine and dried.
SO41 and concentrated to give 1171' crude oxime.

This was dissolved in a 100 rt D-F, and 110 parts of l-chlorosuccinimide was added portionwise at 15°C. After gravity Ω, the mixture was left to stand at 15°C for 1 hour,
The cooling bath was then removed. A rapid exotherm caused the flood level to rise to 50° C., and ice was immediately added to the reaction mixture, which was then partitioned into 1 i] of ether and water. The ether layer was washed 5.6 times with water, then with brine and dried.
, qS0411 so(7 and filtered.

Vinyl acetate (100 gl) was then added, and the solution was heated to reflux while adding 80 g of triethylamine in 250 g of ether over 4 hours. The mixture was cooled, filtered, and the filter cake was washed with water. Washed 6 times and air dried.

This material was combined with another product obtained by separating the P solution, washing the Et, O layer with brine, drying Al9SQ, ), concentrating and trituring with ether. (Total yield, 8a62, melting point 98-99°C).

Example 2 882 of 1,8-soazavinchlo(5,
a, o) Upon addition of undec-7-ene (DHIJ), an exotherm occurred causing the solvent to reflux. The solution layer is aqueous 11CL
and brine, then dry Nα, SO,
), concentrated and distilled to give 522 inxazole, boiling point 75-80°C/1.

Example 3 5-(5-Isoxazolyl)-2-thiophenesulfonylchloride thenyl inxazole in 300 me ether bath and 60 TRf loop tillithium in hexane 1
．． The solution was added to the oven at -78°C.

After stirring for 10 minutes at -78°C, fj, body 5O2 (1
0mel was flowed, and 7 pieces q77+ was room + product chi Yogata'i j;'+','. After a while, a layer of sullefiic acid was applied to the moisture-absorbing hair. Add this to IDO+++(
5 [I C1h In a water tank ^2, 162)~-chlorocone (acid imidization at 0°C) was stirred in portions at a time. After stirring the beef for 50 minutes at room temperature, 4. The mixture was diluted with 200 rr of ice water, filtered, washed with ice water, and air converted to give 20 F sulfonyl chloride, mp 92-92.5°C.

Example 4 3-(6-Isoxazolyl)-2-thiophenesulfonamide 19, A solution of 5 f of sulfonyl chloride in 150 m/m of methylene chloride was saturated with gaseous ammonia and heated to 25°C.
It was then kneaded for 16 hours. Pass the precipitate through, cH, ct
, then water and air dry, 1
1.7PC; l title sulfonamide, melting point 163-16
It was given at 4°C. The Cn, ct, -oT soluble fraction was washed with brine, concentrated to dry N2 (504), and triturated with ether to give an additional 1.52 of the product.

Example 5 S-(S-isoxazolyl)-2-thiophene 102
A mixture of 100 m of sulfonamide, 100 m of 2-butano, 6 mt of looptyl incyanate, and 52 m of potassium carbonate was heated to reflux for 1 hour, boiled down to iK, acidified with cold aqueous 11 Cl, and filtered. solid gold c,'
n, ct, dried, Mg5O4), and concentrated to give 12f' of routinurin. Butyl urea (11F) was dissolved in 4 ml of phoscene in 6-xylene for 1 hour in a 50π6 kiln containing 0.22 of 1,4-soazabicyclo[2,2,23 octane]. 163° CKmM was added over a period of time.

The mixture was cooled, filtered, and concentrated to an orange oil, of which 7"L represents the sulfonylinocyanate.
It had strong infrared absorption at 0 m-'VC. Dissolve this oil (11) in 4 Qrm' of methylene chloride, ff'
1 and used for the next reaction.

Actual sister example 6 A'- [(4,6-somethihebiliminon-2-yl)
aminocarbonyl]-3-(3-isoxazolyl)-2
- Thiophene sulfonamide 6n11 inaneanate 7cn, ct, soluble a (1,1y containing what isonane)
) 0,42 2-amino-4 in methylene chloride of K5i
, 6-dimethylvirimison was added. Bath tJ1. q was removed and the capsule product was triturated with ether and filtered. Recrystallization from t'u30','vflue BttC1 gave 250 ml of product. Melting A172.5
-175°. No VMR (CDCL,) δ2.4 (j, 6
H1,6,76(j, 1Bl, 7.0(ct, 1#l,
7.5 (cL, 11, &2 (d, IHL, 9.0 (d
, 1H1,8,1(br r , 1//l, 10.
6 (bTy, IHl.

Example 7 5-nitro-2-(111-1,2,4-triazol-1-yl)pyridine dissolved in 50 ml of dry DMf'
A solution of -chloro-6-nidrovirison was added to 1c6.9F of 1.2.4-) lyazole sodium salt (90%, Aldrich Chemical Co., Ltd.) in 40 mZ dry D AI F.
The mixture was added dropwise to a suspension containing the following:

After the slow exotherm had subsided, the suspension g was heated to 60°C for 3 hours, then cooled to 25°C and poured onto ice water at 500πt to form a precipitate. After filtering the mixture,
The isolated solid was washed with 2 x 50 ml of water and sucked dry to yield 12 crude products. The product was recrystallized from 2-zolopanol to yield 8y of the compound: h+! Point 131-433°C.

C, 11, N, 0. Nine against VC? ? T value: C゛, a3.9: H, 2, 7: IV, 3&
6:'j46kawaflu: 0', 44.6
; 〃, 2.7: N, 5 6.7
.

Example 8 3-amino-2-(IH-1,2,4-)lyazo 10
D mt: of 5542 chloride in hydrochloric acid, FI ¥ shallow! Compound '5 produced in Example 7 with 102 in L≧t[t] : 0.25 hours 1) : 1) The foil was divided into two parts. After the possible u fever (2so-79°) has slowed down, the suspended enemy is e, 5-qooc 1
Heat for 10 hours, then KO'VC cold for 8jl-6. The mixture was diluted with excess ice water (approximately 7 mxl of KcE, and 50%
Aqueous i'! a (By adding r5 to J II, the layer 76 liquid was made strongly basic to lidomas to eliminate the formation of precipitate +ei. After passing the mixture, the solid that had stopped flowing was washed with water,
Suction drying followed by recrystallization from ethyl acetate hexanes yielded the compound 32; mp 103-10.
5℃.

Analysis vi for C,II,N,TiC: C,52,2HH,4,4;N,a
3, 4: Actual measurement value 2C, 52, 4: H, d5: N, 41
．． 6゜Example 9 2-(1M-1,2,4-triazole-1-i 9f of nitrous acid) Add 30 ml of water I:P@liquid into two IJs.
45m of the compound prepared by the process of Example 8 of 02
8 rinses in concentrated hydrochloric acid and 7 fflKO in glacial acetic acid
A diazonium column was prepared by milling at 25°C. After stirring for about 4 hours, the soazonium suspension was diluted with 93rnf acetic acid, 5.34ml of
of cupric chloride was slowly injected into a mixture consisting of 2 and 37 m of sulfur dioxide. A delayed and intense formation of foam occurred during the addition, accompanied by foaming, which occurred during the cooling process and at the speed of the Noanium Research Institute.
1°Ih・1) field from C.

After the addition, the VC1 cooled I+% was removed, and the soybean solution was stirred at room temperature for 4 hours. The suspended TfJ solution was diluted with total ice water (approximately 800 ml) and stirred to form a solid.

Add 2 x 5 solids to the mixture.
Washed with 0 m/' water and filtered with suction, 17
2 of the compound was produced: mp 128-132°C.

C, B, 0' Z N4U, S V Calculation I
Iσ: C°, 34.4: H, 2,1: /V,
22.9: Tsukito Tsuki direct: 0゛, 544: II,
2.1;A', 23.2゜Measurement example 10 2-(1#-1,2,4-)riazole-1-i12
A suspension containing the compound prepared in Example 9 of Vc15f in tetrahydrofuran was heated at 26 ml while maintaining the reaction temperature at 10-20° C. with external ice-water cooling.
A concentrated ammonium hydroxide water bath solution of nI was poured into the solution. After stirring at room temperature for 5 hours, the suspension was condensed in X air to give a water suspension.

The suspension was placed in ice water (approximately 200 mfi) and stirred to produce a solid. The mixture was filtered to produce 12 tons of product, which was recrystallized from acetonitrile. 8 of the compound was produced, melting point 183-1.
88℃.

Calculated values for C, 11, N, O, S K: C, 37, 5: H, 3, 2: A', 31.0:
Actual value: (% 37j;"% 3.0;A',
30.9゜Example 11 N-[(4,6-somethok7pyriminon-2-yl)aminocarbonyl:]-2-(IM-1,2゜4-triazol-1-yl)-5-pyrisons 10rn! , P
- @fa'flVc O, containing the sulfonamide prepared in Example 10 of K O,5P in dioxane
6F noaznyl (4,6-somethoxy'pyrimison-2
-yl)-carbamate, then Q, 1 of 33f'
．． 8-Soazabicyclo [5,4,01 undec-7-nin (DBU) dead 7'D was obtained.

The suspended Tfil solution was stirred at room temperature for about 2 hours, then for about 75 me
The solution was diluted with water. The solution was acidified with acid (red to lidomas) and heated for 0.5 hours 1'°
When the mixture was stirred, shenjinoi was formed. The mixture was filtered, and the mono-11 It- was washed with 10+++/: of water,
The mixture was dried under suction for 24 hours to produce the questionable compound 072.

5 points 226-230℃.

Cl411.4N, t), S IC vs. j 7-+13
T, y: c,', a 1. a'
, II, 3.5; A', 2 7.6
: Actual value 2C゛, 41.5 : n, 3.7 :
No■, 27.4°JR (Nunoyorl: 1715c
+n-' (C=C)1 Using the branch # described in Reaction Scheme 1-73 and Actual Example 1-11, or any variation thereof, proceed as follows! Compounds in a to 162 can be prepared by IQ experts in this field.

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= =; z u x roe ee 0− ωF
1 (Q n gate
Engineer:! ::
! ::i: 工工工:I::! :uω 工:e:e:! : U Roeeeeeee υwork = 2 Work: I::': Tomoe 2 Self 2 □Ro 2Q Fighting Ro Qυ
ω − for 10 minutes E E E :e:I: 工 === 工
＝ 工 ＝i１ えーえ ＝＝ knee z ＝＝＝：Cz ＝
=:CZ- oar C3-:+: :l: = = Engineering === E - E = = Engineering = 102 2
102: 100 222 and 200 100 zz 8, Otsu 202 100 2 Nishi 2 Tomoe 2 Otsu 100 1:' cgl E E - Ro E E: I: Engineering =
Engineering = E E −α α CI OC7(7(:
F C1+7 cy OF cr cy
cy
Engineering zz self west west 2 west 100 west 200 ZZ self 2u
O = = Engineering −1 N α α C E E E E E E
Ezoo zu= uu z
Ro 2 Ro 2; E E E E E:! : Roe Ee
− = Engineering = E E E E E E Engineering
E:l::I: 工Q I! S
Rb 1;1-15 HC2H3H Q-15HC2H3H Q-15HC2H3H Q-15HC2H5H and ヱO open, CH2Cl-I S 15
6-158CH,CH,OHS 13&-13
8oot, ot, hit 0 14
7-148OSCI-1, Cl-10130-132,
Self-rooster zz 100 200 2 Otsu 2 Otsusu♂ Sen 1:e:! : 工 ω E − E E E E
E E E = α α α α α α ay cy
cr cr cy α α α αe
E E E E:! ::I::I
::e 工 ωuuCJzu2u
"Uzuzu mouth z Oωheichiji J40 0 0 o OOo Oo o v
A ttr u 工 = 工 === え え t-uu”uuuzuuuz
u zu ψ ψ k ψ ro ro ro ro ro engineering:
Engineering = ：″ 2 ω ω 2 ωZCJ口Z 1#′I n = l l:I: r, −I Engineering F−=0ω
=ωU- ri Q lo 0 lo U lo lo lo PORT h^hahah Eeeeeeeee = Q E E lo Q Ro Ro Lo 工 = = υ E E = E E =
d-1+IF-1+1-11- NheheN NNNNN ” I I CICICICICI 7 (: r cycy Q Dan Rlo” x Q-22HHCH: Q-22HHC) (: Q-22HH0CI Q-22HH0CI Q-22) [ CM3C1(: ()-22HC)l C1(.

Q″″22 C) (3CM3C1(.

W22 H1 (CH: Q-22HHCM: Needle 22 H) I CH; Q-22H)t CM: Q-22) t HCM: Q-22) I HC) I.

In the whole table, 4 are indicated by Kimoto. At the end of the book, R11 is CH Yu. death ′′3 '3 QC) [N 0 , CM, CHO OCR? J s R1+ is - unless t.

5゜su 1 η ψ ψ ta η 4 帥 1
Stirrup Kan II to M <'V ('11 ("J
NIN l'Q F'l M P'l F'1 M
IN IN N(M NNIN NNN+l+++
+ l+1Il101 Cr
Cr (y C1(7C1α ay cr
ay ay αヂ territory Yuda bait 愼、″ = E E E = 工 ：I:：I： 工Z(JZ(JL
)ZCJZCJ(J ′z CJ”(JZ(J 工
=
= Working Ω Works = Aero Roie Eee FF1L "L"
M engineering

= Q mouth = Engineering = Eeeee = Engineering Q: r + Eeeee = r N1 hundred 2 hundred 2 hundred 2 □ 2 E E E =
Engineering engineering L) CJ mouth ω (J:J @ Shin da da Shin 41 da da
da da ji da shin ryo shin da
Daji territory 41 @ Daji territory da
bait territory territory da da shin san da da l1111111111111 Todoroki-Hatakesu 2 work e e = z z e e
E Engineering E = Engineering CJ (J (JCJ
(JCJCjCJZ”(J(JCJ:y()
F (7Cr CF (7(IF 0 0r
Cr Or (7α α α 工 =
Work Eee E :': Self 2: □ 0 □. . .

rJI Z mouth Z CJ (J Z ! 工 0 :!:' Flash 工 工 E E E E E = = = RO
- Construction =z x, =□ Self 100 200 zz
ω 2 ω ヱ r) Z (J -日日絭■II 111111 工.

Engineering Engineering = Engineering =: l: Engineering Engineering = ○ = E
E-work E-Eot cy cr α α cy cr
cy cr cy cy cy cy
cy'JtJ'2LCJZz5Z52'fJZ5ZZT
JTJZ=== +111111111111111 === E E E E E E E E L)
:C:i: E E E-1:l::I: Eeeeeeeee Tomoe ==== = Work
= E E - 工 u z
L)z(Jz uzuuQzuZ−″′″ l+ j
+ j+ ″ −″′ −″″″1J”a4 o
o o o o o o o o o
o o o o o o.

E E E = E E E Etsuzuzuzuzuzu ω zuzu
−= E E E E E E:! :el: 工
:I::e:: 工 =E - E =
= = 2- engineering z u z L)
z L)z Lo zQ-CJ CJ C
Jn's circle n i n E E E E E eny=Eroe CJCJL) Low 0 E E E E E E E E E E E E E E E E E E E E E E E N E E E E E E E E E E E E E N E E E E E E E E E E E E N E E E E E E E E E E E N E E E E E E E C J L
Pl circle - bolt 1"11"1 - n,
Self and self,: Hyakki Tomoe and self = xx -F-I M l'FI 1"1 工L) (
J: I:: I: Self-worker = Self-hyakuko = Worker = i n 6 yen - Yen n Bullet gate's Tomoe-Ki-i-Hyaku-oto: Tomoe-Ki-Seikotsu-z = i Bar-Yen - 0e E E = Engineering S - Engineering ○
Work ω Q Work = L) Mouth 0 Work = Work bar
n Yen - Gate PI l"I F'I
M.

Worker Eeeee = Eee = 2 = ωee: II OOOOOOOO(1) (/+ C/
1 (/J (/J (/INl)
100 2: 6 Nishi 2 102 Self-rooster: ″1 ee: I:
E E E E E E - E E ICa"l :
l::I: E E E E E E - E E E♂1E E - E E E 2:2: E E
E E E ♂ Edit 1: I::l::I: E E E ω E
E E E E V φ ψ ψ η φ η ψ
ψ φ ψ ψ ψ ψ η ψ ψ ψ工 工 ＝E ：I：：! : =
Engineering Engineering Z L) Z CJ Z (J
Z (J Z CJ CJ CJ L) Z CJ Z
L) ”(Pi lq 小
M cQ M l”1
Engineering = Engineering:!
: :c :! : Eeeeeeroe Ou:! ::I
::I:EeO○Roe○=-Work=EeE=EEEE L):E::I:
E E E E ω Ro E n of n
1
M＋'Q え え え え
E:I::I:Eroe0-Ro=ωEeekoW=eCJ口Q♂
Engineering = AE=EE: CUEE: I: AE CJ AERO PIF
'l bolt
M M l"1's:C"
E:C:I:
E=u:I::I:口CJ:! :(J:!:EeeeeUωυ 工Q2: え え 工 え え え え ：I:
:! ::E: E-E E-E E1 1
1 1 ψ −φ −ψ ψ −ψ ψ
ψ ψ ψ ψ 1cycy ear b ear ear b
Mimi Mimi Mimi Mimi Table 2b Q Dan 555- Q″″6 HHHCH2O) 13CH3Q-6HC8
3M C)13C)(3C)(3Q-61(C)!3
°)13CM3HCM3Q-6HC83m(CH3
)I C)l needle 6 HCM3C1(3C
)t3C)43)[Q-6HC)l CM
H)I C1(koQ-6)I Hl
(CH3CM3C1(3Q-61(C)t3)t
C) 13 CM3 Cm (koQ-6H
C) 13 C1 (3Cm(3)t CH koQ-6-HC) 13C) 43C) 13C1 (3CM3Q
-6)L C1(3CH3C)13C
)l, C1(koQ-6C)[HHHl(H ENG)I OC)[3QC)13CM S)(QC)(
OcHN S HC1(3CM, Q4S CM3013G)[,N S H0M3CHI, CM 5 C)13C1(30CR,・N5 C1(30CH30CI(3C1(5 C1(3QC)(30CR3N S CM, CM3C1(3C1(S HCM, C) I( 3N 5 CI(3C1(30C)13C!-[Sl(0130C
H3N S = I l l l I l l I
I I l l +81 tongue 2 Otsu 2 self 2
100 2 Otsu 5 z-l :c E E E
E E E E E E +
＋ ＋ ＋ ＋ ＋ ＋
+ + + ooooooooooo.

E E E E E = = E E
E E E E υZ(J(J(J
(J(J(J :ZCJL)Z(J 22LIL)20
2M I”l
l"l F'l M
l"l F'l l"l F'l F'
1D
A
OO, Otsu 26 Otsu self 2 West zz West Otsu 26 2〒 21 E E E E E E E E E E
E E E0 ψ ω η (/10,000
ψ ψ η ψ ω η of ψ
η ψ ψ ψ ψ= = E E E = Work = = Work = E E = = U Work Work
＝ 工（1 poem η η η 1 1 1 偕
l
E102: 100 z z z:i: z :i:
Z:! : Engineering (JL)
CJZtJZPortrait F
'l M PI l"l l"
l ('1 work 2-
= = Engineering Engineering: I::I:CJE E:euu EngineeringQ
ωQO Engineering= Engineering= Engineering xzxxx, E E E E = Q
1+1-1-P'+ l+1 +"q P++-phylum I+
11++6cr cy cy cy ay
cy cy cr cy αcy cy
cy αNlself200 ≧2 Mozu 2 Mozu 2 otsuz″ !+ −E E E E E 02:=
Engineering = =2 E = Z E
E: e: I: 工 ω
z u ” u z , u z u
z u Z LI Z RO ZLIZCJ
,,″ ♂ 工0e え え え ：l：：!： 工 υ エ え え
E U = E E:c O1'Q's bar 1 in 6
0 engineering″′：!： E E E E E
:I:2: 工ええQ 工U ωu :c-u 郎ω
Erotic 2:Qυ:e′1:e” d.

Work = E E E Q Work = E E Ro E E E CJ :c M l'
Q M Inside-E E-Etech υtechu u:cuu-tech 100:! : 100 workers = 100 = 100 workers n:
I:' 工 工 え え え υ 工 ＝ え う え え え Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ possible = E
E E E E E, Otsu 2 Self = 6:2 Tomoe Momo Momo Otsu - Yen,,'II:I: E E E E E E E E E E: Self 2 Otsu 2 Otsu 2 200 2 Otsu 2 102 Otsu Suoto 2
Otsu MM E E E E n Port E E E M
FI E E E Z n600::::Otsu 100 g straw 88
Self 8g 88 Otsu ('11 fi f'l f'l
E E n n Xiao Yen Work E ^ n Yen 6 Work Work n Tomoe Otsu Otsu g8 100 Otsu Otsu Otsu g8 Otsu Otsu Otsu West 8800z
”:!”Tomieeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee υwork♂ +tw'+
:e't E :e E=:I::
l:u:c 工 ：cuuz 工 u え え
u engineering uuu:! '1:e'':C''' = E E - E E u -= E E E
u:I: E E E QF'l M
Pl yen 6:e″
workman. E E: C E E = Engineering U E E: l:! Jee Q erotic zu: cuu engineering Q: I
:′:! '
♂ = = Work Work 3 Eny 0 Eeeee U Loe uu Work Q Rollo Table 2e (Continued) Dan 55 Work”5 ”6 '7 ”8 ”9
'10MW HHHHHHl( Hm(H)(HHHH1( )(1(H)4 HHHHHH H8)(HHH)t HH HHHHHHHHHH MHI(l(,HHHHHH HI-1)I HH)l HHHIn the entire table,
*W unless otherwise indicated by the end of the book.

In tree*books, Wl is S.

Possible, 0M3N c’a oc) 4 CH CM OCRN QC) t, step 3 α 0CR30CH3N CHC) (CM CH3α3N C)t　　OCm(C14 0M30C8,N QC) (30CI4.C)( OCR, OC)t3N CM OCRCH CI (30C) 43N″″ OCHOCRC)4 * O0'13OCR3N''' CH meter club room C1 (3em43N 1″ C1’OCRC)<　1 ° is O.

ri1　ro　00000000　ro　o.

″ : l: ″g Self Self Self = Ochi 100 r J u z u ω cg-1x = Knee; 工= 工= 工=L Pure 工 = 工 ：e :! ::l: Z E
E E E Suku μ West 2 drinking self self 200-:ez5zself-Q ♂ *:c=cz:! ::c:c:cz:E3 ENG:c:c
u: c e ek = e ro e e e: l: u
-υ E - 工 =:I::e 工:I: 工:C:I:EroroeE 工ERoEU1'″'l
f'l l'l'l('I
E-e-e-e-e-e-e: West = e-e-e-e-e-e. . . .

Work ゛==Ex :I:r-E:efWorker=gate fiFl Gate n ″I Pl ′1″ Work E −
E E E” ”::! :uu. . workman
. .

Erotic ωwork υU: Work: I: Eeeee==eeeeeeezeeeeee-〇
〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇
(Jχυ＾Otx”l :e ueeeeeroeeeeee=eee♂ 工Cg+ :!: :E: S :!: :l
: :I: C) :l: 工
ψ η η ψ ψ η φ η η え え
E E = E E
E E2CJ2 (J21CJ L) CJZZ
CJ2aUZCJZCJE E E E E
E E E E E E E E E E E♂ E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E
2::I: E E :l:B=:l::e E
E E E E Engineering E :I::! : workman
E-work ω Work-E-E-Work = Work = = Work-Work E-E: I:E (J Work = Work: I:
:I: 工 -= E E E E E E
E - E - E lηηηη w co ta
Type 1 Ml 2 L) 2 (J 2 ports 21L) 2
1υZtJZ2t1 Engineering engineering engineering Tomoe engineering self Eeeee self ♂ ♂ 11Eeeee engineering Eloeeee: l: ωeeee, Fil engineering: I
：Self-Effect Self-Eh Self-Drinking Self-Effort Section 1 E E E E E = 工 = = E E E E EtA η
η η η η ψ η ψ ψ工
= Zu - Engineering 2CJWCJ
2 ω zuzu color gate Ml”1 portrait n circle i
n = = e e :e:e:l::e
:! ：roωωroωroUU−υ PIF”1 小 靂 F'l 1”l
M M= E E E E = E E L) (Jωω Roro UU construction 1”l F'l F”l l”I PI
MM aw”l:c:!
:Eeeeeeeeeeeet, r'l :i: :E: Eeeee nee 冨===關 :l: 工 :E:2:
2: Emy Es E) 22 Self -Z Otsu 2 200 Suitsu Otome 2 Oto 2 Oto 2 Koki MSIM Pisiimmm
PI M M Engineering
Engineering =
= Engineer:! ::l: υE ero ero e u2: Ro ero e fa'% -1 工 工 = 工 = EE υuL) AE ωU ER OPI f
Q M fQ F'l fQQ10 E
E E E E :l: 工 :! : workman
E-eeee u:e: cuuuu loe uuuu rolo =
E E E - E E E E E :I::g:
e2: E E E E eta tA Mc
nOOOOOOOOtacacacaXcn 工2: u :c z:e
OOOOO017! H&l! I M”r knee’
r:xxx-x E-E - Engineering NIL) '-C
JCJL)CJ4(JL)L)CJ-(JI/1mta
oo mouthoooo o tAwtawww2 Self Otsu Self Dengi = 100 2 Self Mozu 100 = Self 2 ko th,, E E = E E = Ko = Ko Q E E E -) Ll &11 0 0
0 0 0 0 0 m sa ta ta
ta, 2 Otsu Ro West 2 Otsu 200 Hundred 100 2 Otsu 10≦1 E E E E E E E
- ω E E E Eta e o
w ta o o o o o o
o o o ta e ta aa t
a aa engineering=eeeeeroee ieeeeee: I::c:e:I:ee Jt sa OOaa ttz OOtth
(1) OOvz ttz,, F, 5 Otsu 2102
Otsu 2 Otsu 2 頗 工 2::g え え 工 え え Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｅ Ｇ Ｇ Ｇ Ｇ Ｅ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ
acaMOO Otsu 2 Otsu 202 Tomoe Otsuki 2 Otsu 2 Otsu 2 Otsu 100 10 works.

OO&
I ta ta u OOOOta (6u
vz,,&l100 2 □1000 2 myself 2000 2
cgl e e e e :I::C:
E E E E = E E E000
0M rA HrA OOOOuaagWO;
E E E = = E E E E E E E E :l: 工SKI OOO(/1 (/l
(71g/l OOOO(/l l/IN
l 2 Nishi Otsu 100 2 2 Otsu 2 100 Ki cgl 工 :l： 工 え え え
E E E E E = E (/l
an o o o o o tal/I
w (/l OOOOm m e ta2
Drinking Tomoe 202 Otsu Self 2 Self Otsu 202202 Otsu =:
I::c E E E E E E E = = E E E E E) + (/1 0 0 0
0 ta tA ta ca OO
O81 Otsuki 2 Otsu 2 Otsu 2 Fortune 2 Self 2 Otsuko' Work 1 u E E E 2::c E
E E E - = :o tA (
6ra tA o o o o x
m * ga o o m
Wow.

200 262: Otsu 21000 2 Otsuki 2 Otsu 100 600 Tomoe' = Work = E E E = E E E E :I::! ::I: E E
Z L) :I:KOL100OOOOψ ψ
η for η for ψ, 200 2 Otsu 102 Self 2 Otsu
2 Otsu 2 Otsu:! ：″′ RO ET ENG FU ET OE ET
E E WORK E Eooooooooxxxwt
atawoo.

Self hundred words 200 2δ hundred, self 2 tomoe 200 2 self? , :″ −E E E 工 E E E E
E E E E E E E E: II
OOOO(/l (/J t/+ X &
11 &4 t7) t/+N1□ 500 self
100 2 102 102 2 100 2 100 2 100 2 100 2 100 2
E E E E 1o o o o
o o o O(/2 &l') w
m w (1) (/I OQ OO self-rooster
200 2 Otsu 2 Otsu Otsu 2 Tomoe. 100% 2:' J:! : Engineering = E E = E E = E E E E = E E E =) I OOOM
(73&/l M CI'm fi
(/1 &/l OOOO81 100% 2
100 2 Otsu 2 Otsu 100 Otsu, Oooooota tA
(/1 xmca C+2 0000:C
E E E E E :e :c :e
E - E E E E)I N1
1 1Js t/j u OO(/2
(/3 0 0 0 0 (/j (
1) (1) t/)N1102 Tomoe Otomi, 6200
2 self 2 otsu 200.

Edit E E = E E Work E = = E E E = = Work =oo t/1 tA ooc
ntaxootatao.

100 200 200 200 200 200 200 200 200 200 200 200 200
E E E E: = Q E
E E E = Engineering - E E - : C Engineering : I
::+: 工 = = 工 工(1)(400(1)
(/!OOC/)l/100(1)&1lOO(4V West 2200 2 Otsu 2 and 2 □ Otsu 200 200 2 Otsu:!::I:
Engineering :l::e E E E E
=+J: E E E Work E =
Engineering J+ vr o o o ttr o
o o o vz vr trz tt
r o o trz e e e
= E E = Engineering NIL) 1
m x o o x ca ro ro engineering
Engineering = E E = Z (
J Z (J ZCJ zu zu zu
zu z え え え え え え 工 え
= = E E E″11 tZJ &ll&OO
U (/1 0 0 0 tZJ OOO81Otsu2□62102W, Hyakuotsu□Otsu cgl -E E :c2: E E E E E E E E o ta l/I (/1 ca
o o, cav o o o o
u ao as ta.

21 Otsu 2 myself, myself, Otsu 200, myself, myself, 100 □ Otsu = E E
E E = E E XX:X E E E E =
= Work 1 η η's ψ oo η ψ oo
η η O.

:c:e:! : :l: 工 :!
::I:? −11 CJ Z υ 2 CJ
z υ z (J z (J 2 Z
CJml :E: :I: Engineering 2: E E E E E Engineering = Engineering E E E Bai ヂ 41
− − も も bait territory territory xwooo
otaoworaokaaokaow groans
E E E E Pz (J 2 L) u C
Jω0ωυRoQωRoro, :Eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee P※ Homaresu Io Ke Jun o O & 12 Cotton o o 輔 ψ
O.

-=2 100 2 Self 2□ Self 2 and 2. Self χ Q α3

0 Gate 0000Ca(1)g/)g/1001/)
&@0000工 :e:e:! : Engineering
:e:e:! : :ezuuzuzuzuχg Z
(J Z (J Zω2υχ!::I: E E E = = E E E = E E E E E E
D Table 3b (Continued) In all tables, unless indicated by *, W is ・W for wood
is S.

fellow C and 0M (1’H 0M 0M official CH truth CH fee CH* CM heavy CH truth CM heavy CH* CH197-198 ].

I:l OOOOOOOOOOOOOOOOOOZ 2:
:! ::I: Eee Ee Eee F4+
Mouth 202CJL) (J Mouth 21CJ212CJL) Roy i :I:″ Painter E E E E E = Work =:!::C Work ω
Construction roller r-1r-I P41-, I A +-1m
t-4+m A 'r4 e-4-1,:'' EE: e: I: AE = AE 2: ω ω = l P
4s o o o o o o o OQ OOO・ENG =
E E E E E N1υrJtJ
ZcJ2ω slot 2ω slot 1 work 1: e = 2eeeeeeeeeeeee ecoOO-m -I A m m-m F-I S t-
4F4--0! ::I: Fu ω 1”l
, :Cself===eeeeee=eeeeeeee 1:I OOOO
OOOOOOOOOOOO construction area + ZXX eeeeee = ello = 3 α a α α ay cy cr ay
α α α 0 α-+-t I-I P45-m4
++1 ++ ++l ++ ++1-s 工= 工=== 工:l::c えええω 工#al 26. Self = Self 2 Self = Self = Oto Mengaku.

Pure E E Engineering E :I::S::I: Engineering :C
Work Work E Q E:,,:Self, Etsumi: Self 2 Tomoe 2 Self Work Otsu 2 Self.

E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E f 工 工 == E E E E E E E E E 2::c 工 工 2: :c
Eco II OOOOOOOOOO(/J tA
(1) tAeeeeee
= Engineering = Engineering Engineering NIC
J 2 CJ 2 (J 2
L) ω zu υ ω 1 ωc,″
Heat engineer:! : E E 100 = E E E E E E E E E E E E E E E E E E E E E E E E E E E E E E − Q
Work = = E NN hehe NNtN tN
IN 1N IN~ 01 CF cy ay
cy cy cr cy cy ay
cy cy ay c [(/l t/l (/
l (/J l/J (/J (/J (/J H(/
l (/J OOOOOOOO= E E
E E J::! ::e :l
: E E2L) (J21L)2CJ
ZL)L)ωU2CJ2ω≧01”l F
'll'Q l”1 工 === え え uxu L) xu :I
: xx E E E E E E F'
l F’l Ml”
l
I”1==
E E
工 え − ω 工 xu
xuu E E E - = E E
E 0 engineering = = E E E E E E - Ro E E
E-E E E-E ~N N NN NIN N
NNNFl l"l t"11'Q l'l f'l
l'Q・-1111111111111111CF
(F cyCF cy(70F OOr D
α C7Cr Cy Cy (y α Q)
II OOOOOOOOOOaa us n tt
s us cn ta u, Z r3-5
□ Otsu 6 Otsu Otsu 26 □ Otsu Tori 2,, vl , 5 Ko Otsu 100 Eeeee 88 Ee Otsuz x 5”P'I n - Koukou 100 Kou Otsu Kou Eeeee Otsu Eee Ko 01 Fortune reading 6 Mimi 6mi 6 ears 66mi&=; )I Q-9)IHH14 Q-9CM3C1(3HH Q-9Hl(Cl-13)1 Q-9)I HHC)13 Q-9H)l CH2O)13 Q-981(814 Q-9HHH)4 Q-9HH )18 Q-9)1)1-HH (>-9HHH) (Q-9)1M)1)1 Table (continued) OCM CM - CH33 0CHM - 0M33 0CHC) (- CH33 0CH30CI3M - CH3CN, α - CM30CR3N - 0CH30CI(3C1(-CH3QC)13C1(-CI QC)120M3C)i -CM(
OCH) CM-0C)(332 C)I CH- Ml(CH(C1() CHC)(-C)10-n
-CM Ot C) (-S-n-
CM CM CM -1 49
3 S-n-CHCHF CM CH--Eng. 2:
E E 2:2: E E E:! : E E E E E6□Self 2 Self Otsu 2 Otsuki 2 Otsu 2 Tonguezz
, ZE E E E E = 工 uu え え υυp2::su口ω 工 え え
E 工 え rυ 工 U − 工 υ 工 uuxxx 工 υ 工 = knee
workman.

Eeeee Q Eeeee: cuu: I: Eee = Roeko ==
Technique Mozu Himself Tomoe 212 ・Ml (J 2
(J CJ χ ω-1= 工 = AE =
Work = E - = Tomi Work E1 = Work = Work ==== Work = Work = = Work -1 Zl (J t shi Q ='r: [ cm”l :e * E E E Work E E E =
= Engineering = = Engineering 1 E E = E E - E === E E E Eo1 α cyay
:y α こ α α α α こ α α α−−
1,1 r'Iself =:I::I: E E E E E E E E E = E E.

Dark ILI-:: :! ： 工＝E
E E − E E E = E E
E E E E E E E NI C
j 2 L) 2 L) 2 CJ 2 (J mouth υ21
(JIJ2CjI!AE:I::I:EE= 工= EEEE′ 匡１ RO ＝ 工 = 工 え = 工 ===
E E E E -゛ E E :I:
:e :e Engineering Engineering CJ (J21
CJ211J2 (J2CJ2121: a mouth ZCJCJ2
2M l”1 cll え え Ｇ ＝ 工 え ー ＝
Engineering -= Engineering = ω υ ○ E E E u u
○ Work = bolt bolt circle M
l”S Color = E E =
Engineering 1 engineering ==== E E L): eCJ (J
Engineering = υ Engineering L) CJ - Engineering I
Work E E E E E E E E E E Q Work E E E E OE -Ro O E E E E E
E = Engineering = 1-JICJ2I○21CJ2L)
CJ:ZIL121 (J(JL)L)2, -0 Cg4I:I: Self = Self E - E - ===
= Engineering♂Ueeee.

cgIeeee ωeeeeee==eeee= ゚ 0OOOOOOOOOOOOOOc6cqca===
E E E = Engineering i0 2
zuuuzuuu: +sL): a2uz gate n
Yen (, I
M x: xx
==
xxIJcJcJ-RoU-Eeeee=Any=Q口EeE=E
E E E E E =NI L
) 2 CJ tJ 21 (J 21 Cj 2 (
J 21 J
= Engineering E = E E E Engineering
E: C: C E E Work E - E Q - Work
= E E = E E E
= E E E E E E
X: C Engineering Jt OOOOOOOOOOOOOrAC/l l/
I ttx ttz ttr vr= 工 = E - E E E E E MI
CJ 2 CJ CJ L) Z CJ L) L)
21 CJ 2 L1 2
workman.

cfal -E E Q Engineering = U -E E E E E U Engineering m +-+ l+IF4
+-t-F-I F-11+1--1+I ++11-
1 p-t l-I P-IIN NIN IN NN
IN NIN FJ IN N IN IN NIN
Notcy Mi Mi Fortune 0 αααα αα αααα
α α000000000ca rA cqca
.

K' Ko Yuji 1-P )II η xc6ta η (/1(1)+
111 hair [( @ ヂ 愼= e - xx :e
：e xZCJ口21(J2(JroAro20
≧mouth FPI
M engineering ・ engineering engineering === engineering = = ω engineering engineering = engineering
= Article 1”l (ri ri [((4#?
Eat -he NIN~hehehe N to NNhehe- α α α α α CYCR α α CYC
y α α α da da da II Bait ji
Shun Daishin Shinshin De Da Da -Da -Da -Dai: Li ++++++++++++++
1 ++t1 Eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy tae tao ottoji
Ji da da da da ji Shin ji da
Bait da Shin ji ji jida ji @
Shin bait reconnaissance da ji ji ji bait bait reconnaissance bait hehe engineering = E E: CU E E E E E E engineering
= Engineering =HESS:g::::::::: )l l l 1 1 1 l
l l l I I I
I II I l-626□52: 2 □
Hyakuotomi rooster Hyakuotto 2 □♂ t1 Kototo Tomoe Hyakuto Hyakuhyakueeee = 2 = Nishigodama! Bait-II
da 11 value 41 da reference
da v 愼 bait 愼 territoryg*aa da
Bait III Da Bait Bait Bait
San - Shin 5 Hyakuotsu 2 □ Tomoe Tori Otsu 2 □ Otsu Hyaku 6 F D (r D (7 (7D D (F
D α e D Cr (7d
E:! : :c
:cNl ω 2I u 2I uz
Mouth (J22L): WIU) rP1 color n+”'+ F'l
l'new'+x え え え MM:I: の工 n 工
To: (J(J(JU え え ０ 工
ω 工（J（JIMI OOOOCJ CJ O
CJ OCJ OO1■ ζ (h ■ C
■ Q ■ ■ ■ か (He~he IN NIN to NIN IN to hede α α +7 Cy
α α α I:ycy ri α hikoku=
E E = E E E E E E E ILL)CJ2CJ2tJ
CJ2CJ2tJ2t)ZCJRorotsuC'KO1'1F)PIl"1FIF'l('+1'QEEEEMMF'lF'll'l('
l engineering: encqm e e e (JCJ(J
E E E = E E R O E
E○○L)OOOL)(J(J(JCJL)OO
L) L) L) Elle e e e = p:
r″:C″::! :! :I::C: [(J:I:LIC
J(J:e:I::I:S.

s'%5ll-〕-Ko-Ko]-riψ-Roku ψ-ko ψ-
Cor) - Cork r++IJ4t'Qt"lF'1Mt"
11"1MM1"1MFIPIPI+"11"lF'1
M1+1111111111111+11 Reno yααOαααC ko αC] - ααC ko [(ko 1 α(
Koichi ααχ 工 工 ＝
Engineering = Engineering 8121 ZCJCJ2C
J22u:ILL) uCg+ :e: =1::e
=e E E - :e:+:z=e 巳 E'J::I: E E E E E E E CJL):ZICJ2L121L)221L)
* L) 21 口 2121 工 え え え え ＝ 工 ＝ え
Eil:! : Engineering Q E E E - E
E E E E E:I::c
Engineering = E
E=CJ"2U2'2u2CJ202U220CJ
2= E E E E E :I::! : workman
E E E ω E E E E E:! := E E −
E Engineering MI CJ 2 (J 0 mouth 222ω2
021CJ2= Agony 1 = =u E E - = Engineering = = Engineering ;== E E - E E E E212121C
Jω2ω2CJ2tJ22ω Koguchi = Ri - = = E E 1111111111

n=
Engineering = u: I: Engineering = = E E E E E υ E E E =,' rg+ :e x Engineering = = Q E E E = Engineering = Engineering === E E E =
Engineering (J2C) 2 (J2 (J2 (J2L) L) (J2 (J
21"l l"l l'l l"1
Work x
xu -xx,'r, :r:u CJ o Engineering Q
Work circle n circle portrait M F'l l”1
The beginning of the story. Engineering ==== Engineering: C Otsumi Tomoe E ω (J Engineering! (J: [(J(,)○U Roro FI
Ttsu cqesu = 0 eeeee self rooster tomoe.

1: l: ″ uzz: cuu
RoFI I+IF'l (
””+ l'l ('Q Fl ('1 c'I
F'l ('+ 4゜゜゜゜えーーTomoe:,: Tomoe Mozuko Mi Tomoe = P 0 Eee 1 工':l:″′ Anatomy: ○Ee○ux:!:l-3Eeee○ ω-.

1” 11 works ==== Work === E E = E E
= Table 5a (H) 18 H) 1! ( )I H) ()l) I H8 continuation) OCl(3C)l(QC)L3)2M H CHCH3 ”310 0 0 0 0 0 0 crr rt
r (/l (7) ttr vr ch
ttr C4ta = E E = E E E E = Engineering = FJI (J
ω υ 21(J21(JC, 12cJ21cJc
JZL) 2CJ Eng.

II engineering = E E - = xx=x= E E
E − 0 Knee 1 E E E === Eng ==:
E E E E - = Engineering = n c, : l E E - E E = E E E - E = E = S = = n Country 1 Engineering = Engineering = Engineering = S Engineering = = :C
z z え ＝ 工 ψ ψ ψ 1 ψ
1 − ψ ψ ψ ψ ψ ψ
ψ ψ ψ ψ輔 η tAtA φ η η
η ψ 0 η ψ η ψ= = E
E E E E E21 (J21 (JZC)
JCJL) CJ21CJ21 (J21n = 工 = = 工 = 工 = 工 ：+： :!
:: Engineering ψ ψ 1 ψ ψ ψ 1 ψ ψ
−−ψ ψ ψTable 5b (continued) Q! "3 'A" 5 ~55Q-6HH
HCM3CH3CM31 (Q-6HCHHCHC)I CM C) IQ-6C
)l HHHH)I H0CH30C)(, CM
S QC) 130CH3M S CH3 tap 3C) us CK, CM311 3 C)t QC)I CMSCHOC)I
M s 0CHQC) (CHS QC) (QC)l N SCHCHCH5 CMC) [MS CHQC)I C) Is CI(0C)i M S W l l l l l l l l l
l l l l l + 1 1 1
Field 52 West, 52 Self 2 Self 2 Otsu 2 Otsu 2 Otsu Ototsu G-'' = Work = IX E: C E E E Self Work Otsu Work Etsumi Tori Self Work Self Nige 恢
- + l l l I OOOOOOOOOOOO
Tomoe Mozu 2 Otsu Tomoe 2 Otsu 2 □ Self West 2 Self 2 E E E E E E E E E E - E E E E E E E E E E E E E E E E E - == E E E E = 工Work Eeeee = Uro υuu Roro υ Work 5IF11 - PI F'l FI I"1
1”1 Eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeoooooooooooooooooooooooooooooooooooo N46- 5555-K5 ==55 = 5=?
Engineering ψ Mg4a/J Trout ψ 4 -
閤 - Seki 4 閫 fungus group - cotton
Nui Otsu 2 Otsu, Otsu 2 100 2 □ Otsu , 2 Otsu 2 Self 2 □
Otsumiko 6 work χ ee ee ee :I:2:r, :c
E E E E E E υ Engineering EEEEEEEEEE EOL EEEEE: llK11g
6(/II/3111111111= I Q %l :e = E E E - =
= E - E E =l+F11+/-
'JL+/ ri 1. / 1. / l+r 1
．． / J −″ α 0e − =
Engineering 2I 22CJZCJ2CJ202 = Engineering ===Eeeeeero α cyCP c7 (7Or CF CP
CF Or Or:I::I:
E E = E E E E 8102+○2I2I Loros Qυsu ω book ω evening Lose.

Cgl e:e:c=:eu=! : E E E E E E = E -E E
E E E E
= =102U2CJ202C)2CJ2CJ
Portrait of 2u
n-e
E engineer ee Oeeee eroee ω n Port 1”l l'
l
E = Engineering Engineering u:! :
u: p: c engineering Q engineering pur+: lo e
B 0 portrait
1'P1t#1=
= Varnish U:
c E E - E ω Work = = Work 0
Engineering Sumi 1”l M
I"l l"l
PI's work = work
=E E -Work OωEeω=EroeL):CL)CJ Work
Portrait -1=
= ee ee −:
c o -e e e - ro ω 工
Technique =n Color Portrait
Portrait Fl l”l
f'l 小 ＝ ＝
E E E E E =
=ω=Ee○Qlow=Work0ωUUU ====Work=E E=E E E E −
Engineering? 41 m CJ 2 CJ 2
CJ 2 ro 21 (J21 ro,, 1'.Iself rooster self self 100 work 100 self e self ot self t5eee tomoe e e tomoe e e e tomoe self e, i<1
, Eng. . = ω engineering L) (J...

FS M PI l”l
F'l l"l l"l l"1=
E E − ====口１ 工 = E E E E = = E
E = Engineering = Engineering = E
E E E E E E2C
J2CJ'2CJ2CJ2"J'21: J2CJ2'J
ω ωOrtsu i
Circle #Il”l Bolt Color E M
l'l l'l mon ee shaw --=
Work = υ U Work = E E CJ (J Work
S Erotic UU Rolo QO Rorooo Mouth Q Mouth rF11'lF'lF'll"l l"IM
f'1fQl'1e E E = =
E E 2- Workω ω L) ω ω Work ω U Ero Q ω Work E M M
F'l F'l F'l F'l M
M l'l 1"1 1"I M
F'1= E E = E E =
E-:I::! :=ωlowUlow, 00gu0suUee1 Gate Gate t'QfQ
M yen i n e. Eee, Tomoe, Kōki
Kimihyakue E = West Gate PIF'l Gate n.
Port - Gate n Port Plf'1 Mini
E = Engineering = Engineering = = Engineering = xr:
z'xroυωuurie0ωmouthωCJ
Bolt 1-'11" 1 yen Mini
= E E E
E E = Work E ω Work Work = ω
ω = ω Work Ou Q Lo Q Work Sumi
Portrait Portrait 1”I FIF'l
Lock gate Port gate n Port circle =
E E E = Engineering = = Engineering =:
! : E ＝υ 工 ω UU＝ ω υ
uuuuuuguzzP'lPl - Yen
- Gate n Port Gate = = Work x =
:e :I: x =]mouthI+)ω
:! ::l::l:L)CJL) 工0ωnee= え え え え え ：e =7− == 工 ：I：
Engineering = CU E: JI OOOOOOOOOOO
OO E E E E E E E
E MI L) 2 CJ L)
CJ L) L) u 2 (J
2i? Agony ``1eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee self :I:,:,I
Cgl :C:e :e :e 工 = =
z 工 工 = knee ♂
Engineering.

E E E U Work = = E E E Work E 0 E E = Q Worker's Portrait n
The Portrait of = = E
E-E-E-E-E-E-U
υ varnish L) T, ω ω 0 ω ro 0 erotic ○ ko 0
Work′ Work = E − υ =
E E − = Work ω Work :! : Engineering Engineering L
):I:(JE1”l PI
F'l M ('l's i gate
n = engineering = engineering
workman :! : E E E == Engineering Q
E E Lo -■ ”r:u:I:u ω E Lo ○ υ 工 Q-0E E E
E-work 已 E-E = = E-E-U C
J E E E L):CL)-PI
F'l's n yen n a -
E E E = E E E E S Engineering = ω Engineering U Eroe υ Roe E:! :Oωmouthω8-
・° ♂ ゛.

Q E E E E = E E L):c:! ::I
: E ro E E E ω E = E - E E E E E E E E E: e2: E
E E Nil OOOOOOOOOOOOOOO (12χ
E E E E E
ENl 2 CJ 2CJ 2 υ ”Xt
Jt) 2L) 2u = = ; = ♂ ■Work: I: Otsu Otsu wo 100 Eeeeeee = = ♂
1 Tomoe Tomoe Self Rooster Self Self Self E E E E E E -o
=-1:l: CJeeeeee. E=Engineer E=:I″′F
” 11KiOtsuKiKimiKiEKiEeeEE -♂ -；EE 工 え え：I:L） -工 工
E E E η ψ tA ω's η 喰
η η W 的 ψ ψ ψ ω −η工 xx
x: x x e e
-2L) 2L) ZCJ CJ uzzuzuz mouth Z
CJ= E E E E E E E E
工 え え :l:：I： 工 工? E E E E E E - E E E E
E -Ko U: I: E: C ″ Ema Erri Erd =.

= Any = Engineering = Eeeeeee CJ2: Eeroe E E E E E = Engineering E E E E E E E Q Engineering I ゛Eeeeeeeee = Eee = Eeeee == = E E E E E E E - = Engineering Engineering: I:
:c E −′J1tArA η ψ η η η
φ ψ ri Seki ψ η η η ψE E E E E E
ENI Z υ 2 CJ
21CJ 2I tJZCJ21L) 2Z2CJ-1
Engineering: eeeee. Engineer. Eeeeeυtech 1'FI
M
PI
− Ni E E E E E = = 工; = E − E E E η
ψ ψ c71 η η ψ η
E E E ZCJ2CJ2CJ
ZCJ n - Yen Port n n 6e E
= = E E E CI) Ro Q Ro υ Roero = Eee:! :Engineer Roe===E − E=
=Nl (J Roro Fuguchi 2!ω2010CJ2a=”l
=eeeeeeeeeeeeeee, '211 construction = =
E E E - = = E E = Work area■ Work -
= E - E E - E ===== Eng
= = E − Eng
Engineering2ICJ2CJZCJ2tJ202υNakuguchi≧Q
z(”1 m PI
M l'l l'l (Q M
Fl==== E E E E E E E R E = R Q Roe ω Roro 0 mouth n Port Port
M M fQ=
Engineering === Engineering Roeee = Roe ω Erotic Erotic 2: Q Engineering Fl fQ l'l
l'l M +'Q's = 工 = E
- = = engineering = engineering CJLI loe = engineering = υ loae Q loe yen +'l l'l M
Gate 1”'l t'l F'l
F"l M yen: 0 eh 100 100 100 100 100 100 100 100 yen!: 工 -= ＝ 工 x"xx:x:x：E
E = 工 31 ■ 1 ■ 000000
000ONl 5 Z (J SelfFJ Z Z Z Z
z zu z Q2 (J:I:″′ (1'″′l 5 5 え え え え え え え え Ｇ Ｇ Ｇ”l :I: r:c :
! : :C:l: x x x r: x x z:
c
−E′ ni Straw; Star Engineering 2: uueeeeeeee υQ− = 工 o o o
o Oo o o o o o o o o o o o
M l"l l'l portrait
i no n: c: c
n-e-e-e
E E E U υ E E E E Ro U E
E E U υ Work U Work E E − Work =
E E E E E E = Engineering E E) I OO
Ot/I I/! I/J t/1 14 +
/) (1) Z (/l (1)
cal, ″I:l:Eeeeeeeeeeeeeeeeeee:
-Mon-n 21 E E E E E E E E E E E E U O;
η ψ ψ η ω φ ψ い ψ
ψ ψ η ψ ψ＝ of ψ q
E E E E
E = =zcJzuz
ω zu Z (J zu z ro
− υ ZF″l F'l
F'l 1"I M
l'l F'l F'l
F'1e E
E E = E E
=0 e e e L):! :(J:CL):l:(J
L) Ero - UUFi
＋”IPI
n +'Q FI PI
FI P+5Eee Tomoe Otsu SelfEeOtsu Otsumi E Nishi Hyakumi Otsumi = E E E E E = = E
E E E E = Engineering = = Engineering caX
caoooooooo I4 WUHtaZ100 2z Otsu 2 Otsu 2 Tomoe 200 2 Otsu 2 Tomoe 2-yen,' Roeeeeeee engineering: I::l::! : Engineering E: r+
c12m Rorororo 0 mouth owwwm = Eeeeee -e =
== Field 200roQ2ωQ口UZ口V1ψηRororororoOo oψφψψηηE 2 ω Ro= === E E E E° u=c
:e:c:e 工-sa sa o o o
o o o o sa sa ta
ta sa♂ -E E :X: 工 2: E E E E Q
E E E E 44M&? 00000000mm Kusunoki GI
IM&a Self 2 Oto Tomoe Otsu 2 Otsu 2 Otsu 2: Oto Mami 2 Otsu 2 Otsueeee Tomoe °eeeeeeeeeeeeeeee if HOOOOOOOO
OtA tA &6 Els C = E E =
E = = Engineering N + = Low uuzuz
uulowUU 工′匡1:! ::! ::! ::I: E E E - ω
====atAoηηroooororoO'ηηηψψ
ψ2 Self Tomoe 2 Self 2 Self 2 Self 2 Hundred Self 2 Self 2 Otsu□Work' =Eeeero=Eee=Work=Work=Eeeeeee: JJ & a ro oaasa ro 0 sekikan 00 ψ 2□ 100, 6 ot, d ot
, and = Otsu 2 Buri E E E E E E Work =
E E E E Eooooooooow &+2 &
4 I4 camsamo.

Otsu to Otsu = Otsu 2 Otsu Otsu Ototsu = 100 2 Self 26 Otsu 2 E.

Varnish: CEEEEEROEEROEEEROEEEROEEEE: II O
Ovz (/2 th (/> 0 ro)
oowcaw ee ee ee
Engineering ===NI CJ 2121 (J
U CJ 2 CJ 20CJ (J21cgl!
Z: Engineering = E E E E E E
E :cnOOOOtA coWraOOOOOWfi
caVOζ E E E E E
E = = Engineering -= = Engineering
= Engineering) I OOOtA X ta c/+
OOOO (1) C4 (1) Engineering = E E E E E = Nl 21 CJ
CJ (J 210202ωQ口L) 2nd work 1st work E
E E = Engineering = E − E E E E = η
B 000 η φ η η oooo η η
ψ ψE E E E E = E
E E E = ro uzuzuuzuu
zuzu ω 2LIL) = E E E E ===
= E E E = E E E =-I (/l
OOOO(/l C71(1) C7) O
OOO(/l I-E-E
E-e-e.

-10t+)21(J2CJ2(J2L)2(J2(J
.

♂ Agony 1 Roe = = Work ==== E E E
E0 η IA 0000 rA η /ZOro
ct>u'l OO8 Tomoe 21 Tomoe 2 Tomoe Tomoe 2 Tomoe 2
Tomoe self-self-engineering.

= = E E = E E = E - E = Engineering = Engineering U -:lI OOOOOOOO(/+
C/) CIl Z l/) (/l
ca I/! :I::c E
E = = Engineering Nl
2 L) 21 CJ (J 2 L)
(J 2 U 2 L) 2 U = -1 d = E d = U d = E d =
E0000000cqcaZtacacacaO
OO engineering.

U E E E E E E :c:! ：＝E
E − E E = E″II OOOO(1) (/
3 (/3 fi l/) H(/3 (/l OOO
O-tech :e:! : E E E E
=== Knee (10 (J (J (J mouth 21C)
J2L) 210CJL) 2ICJ 工 工oooocatAtAtAcamwoooo.

==2: Engineering :I:2: E E
E20zuuzuzuuuuuz 2Goe E E E = E E:! ::I: E E E E - E J+ o o o n u E/3
vz ttz M tt> (/1 ro o o o.

:! ::e:! ::e:! : :e
E E E E NI CJ CJ C
J uω true muddy ro 21CJCJ (J21υ2O roro (/
2(1)X(/1(1)(1)(4ro000:I:
E E E E E E:!
::! :ω 2I u υ 2I υ A ω υ
ω Q χ ω χ工：! : E E E E E E = 工 工 ：C え え:)l tj
) (/J (jl t/l Oro UJ
tA OOOO1= E - E
E E = □? 41 L)
20CJCJ21 (J2IC, 12 (I21)
E E E - = E E E - = Engineering.

4 cn w tn o o z ta
o o w ca (jl OOCI2
xo.

= Engineering JZC) 10c: e: e Engineering = EEEEE = Engineering = ROEEE =) I
(/l rAOOl/J t/l OOOOZ
+/nij:l::! ::I: 工 2::c
E E E E E Et/2 k 00 η ψ
00 ψ η 00 ψ ψ 00 η η
E = 工 ω zu υ ZC
J2CJZtJ2ZCJ2 ω Tomi 0 Sloe
E= :e E E E E E :! ::I::H
E E E E E ENG)l OOOOt/l (/l
(/l I/J OO(/l t/l C=
= E E E =
=8(02ω 21L)21(J2+ 02 Q χ
Hcgl E E - E E E E E
E E E Go”0 o 01/II/3(/J(/
3001/ml/JOOM(/JOO(/3E-
E = E E E
=^Ro: IICJ21L) 21CJ21CJ2102t
J2Mωs: II I/l OOOf/l
OOOOX C71(/l (/3cg+
-E E E E E E E E Work E E E00McaOOOOV v
l HHOOc4caOOe
E E E = Engineering
ENG (J2I(J2CJ:ZICj2(J2(J20
Tomi Ross Qz Engineering :I::I: E E Engineering E
E = E - E E E E E E)1
η Kamuguchi Q ttz tAOguchi or Aooo.

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ω E E E = J α α r ml OOOOOOOO(/l f/l (/l
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= NICJ210 Roro 2CJ2+2 (JCJ21CJ2
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l FI PI f'l 1”l
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η's evil η η η η η cut ψ η η
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= =21(JZU 21CJ2 2I C
J2CJZL) 2ZCJ (J Engineering.

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E = N + ≧ mouth 2CJ202CJ2u2CJ2:' c, alself, Tomoe, Tomoe, Tomoe, Tomoe, Tomoe, Tomoe, U, U, U, U, U, U, U, U, U, U, U. . . . . .

F'l
M l'l ri==e
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sω1ωωQf'l Fl cQ l'tl
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E = = = Engineering Engineering E = = Engineering −ucJRoυ
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I = = E E - = Work Q Work = E E E: I: E E E ω 0 Work 0 E
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n mini. workman'
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E = = O engineering = = ωeeeeeroroe CJCJ-
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E = E - :I: E E E u:e:c
E E Q E E E Q Engineering I#11'l
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M PI F'l FI Engineering =
E E E E E = = 工：l：：! := 工○ω 工QQEEROROLORω ＝Roro= え え ＝ え え え え え ＝ 工 工 富 え
E E engineering E ml OOOO RO oooooo RO
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碕 η η η ψ 碕 η η η η＝ 工 ＝＝＝ 工 −＝
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E E E - = 工 -:I: E E == = E E - E :I: x'x:xx'x
:x ω E − == ==== E E = E − = = E
− E = Q engineering.

E − E ==== E E = E E − =
Q −:′ x = xxx 工 = 工 = 工 ==
== υ 工 == E E = E E E
E E E = E - E - = 工”II I
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E E E E Nl 20
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= Ezro 2I2+2021CJZCJ2CJ2
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l PI Fl tsu h yen 1j M
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no n gate e
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M FI Fl fi FI E E E E E E E E E E E 0 units (JCJ
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l'l F'S F'I PI M PI
FL E E E E = E E
E = E E - Rororoero ωυωω Roro ω Erotic = Engineering = Engineering: c: l:: I: E Engineering Engineering E E O Engineering : e: l
: E E E E Eero Q mouth 10 ≧ Q Lecture mouth 20 ω = = 11 E E E E E E E E E E = I CI″l E E E E =:!: E E E E E E E E ago l E E E E E E E; =
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t"I M l'l M l'
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:+=Eeee ω0 Roe CJ(,)(J Rolo M
c'l F'l F'l
l”1♂ = E E
E = Knee = υ = Eeeroero = υEroe construction worker E = E −
=Eeeeeee LIL)LleeeeeeQLOEEE L)(J
n 轡 1”I PI l”l F
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Portrait = E E E - E E
E - E E Eeeee U Eero U Roro U Eeroro υω
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tA η's ψ η η ψ ψ η
E E E Nl 2 (
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2 υ 2,,' CI: Ie E E E E E E E E
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cgl - Engineering Engineering Engineering Engineering Engineering Engineering E E E E Q Qcsccrcycrcycycyc
ycy cr cycycycycyrA ψ
v tA ψ ψ η η ψ φ η φ η η
ψ ψ η ω102 200, 2 7 200, 200,
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M (”I PIFl Yen
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:e 工 工 え ωω え え Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ Ｇ う:euM M l”l F'
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Q″″41 HCM3HC1 (3CM3Q-41H [
(83C,C) i3CM3 α3Q-ALCM HH
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η ψ η ψ ψ η:I::! :
= E E E = E -CJ
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E Ml 2 CJ L) 口2CJ2CJCJCJZωQ
2nd grade.

:g1 E - E E E E - :eu -
E E E E E -c/IC/I Ro 0O
OOOOOOca tA WcataW= Eero=eeee:l::l::l::! ::! := 工=)! I C/J OOfi (/l OO(
/I Ia OOZ H:r::! : Engineering
＝ 工 ′:! : Engineering Nl 21■
Tomiguchi (J2CJ (J202CJ2cg+ Engineering = Engineering Engineering E E E E E E E: e: +: z0000
0000(/Ic/l(/J(/IZ(/l(/1(/
300 = Engineering = Engineering =, Any Yellow = Aeeeeee = :ll O
O(/1 (6ra ta o o o
o ta ca ta:! : x
'x E E - E Industrial Complex (J21
21L) RO L) Z, CJ 2 CJ
L) CJ 2 to 1 E E E E E E E = = E E E η口0OOtatAZV
OOOOtat+'>taV.

Engineering = E E xx xx
x ”r, = xW mouth ZL) QCJ2Nω mouth 20
○CJ2υ0u engineering = = engineering = = E E E
−= E E E E − E Work) 100 φ η of 0 000 η Cutting = Work −= = E −
Engineering? J+ 21 CJ Cj CJ 21 CJ
2 L) 2 Lm (J CJ mouth flash 1:I: =
E E E E E = 工 E
E E Seki ω 0000 η ψ η ψ
B o 00's ψ η ψE -
E E === E E 1 book υ uzuzpuz ω 0 Tomi Ro 2, Ro
21L) L) E E = Work E E E E E
= E E E = E E E “Jl c12o
omouth0taWcoHOOOOW= 工 ===
= Engineering = Nl (J L) 2
CJ 2 CJ 2 (J 2 C,
l 2 (J 21 L) 工' 210 Eeeeeeeee = Eeeeeee Aη0 Rorororo tAψηη口0ψψ0 Roe E
=== E E E - E - =21
CJ2C,12(J(JL)2(JCJ:ZICjCJ
CJL) L) = Eeeeeeeeeee = Aee = Eeroeshi0OOOOOWZtarAtnc+'>cocao.

E E E E :1::e E E - Engineering Nl 21 L) 2 CJ (J
2 (J CJ 2 u Z CJ 21 CJ L
)CJoooooxca rA caxcaWOO
O = E E = Engineering ===
EngineeringU2U2suL12u2uL)21ω2(J
♂ E E E E E E E E E E E = E E =5+ 0 0 0 0 ctx tAtt
z ttz tth ttz vz ta
Oo += E E E − = E E E =.

N1 χ ω RO ω ω RO 2 RO 2 LOS 0 ω ω 1 work. E'III E E:e (J:e E
- E E E E ω Engineering) 00000t/l (/l
(/JV(4(/11/loo ro 0, 100 2nd self Tomoe 21 100th 2nd Tomoe Otomi 2I 102nd work.

= Engineering = E E E E E E E E = =
工 = 工 工）I OOOψ 輔 η ri η
ψ ω η 0ONl Tomoe Nishi Otsu Hyaku □ Otsu 2 Otsu 21 Otsu Mozu:! ：″′,″l cgI −E ω 工 = え え ＝ 工 ω =ooooooow tA cawwca
w o b 0.0 e = e e e e e =2I
U2CJ'ZCJCJZCJ2ωω UUZ口2e ：I::! := E − E E E :l:
E E E Work E E ψηηη口0ψψooo
oη(E E E E E E - E1-JI CJ 2 U mouth L) 2 (J202ω2CJ'
Milk ; Engineering E E E E E E E ===
kooww Roro (/1taOOrAVcaOOo2HOO
Engineering Engineering = Engineering = E E E =
Engineering = =ZIL)21L)2CJuCJ2(J
L) Mouth 2sL+2CJuU:l:″E E - E E E E E E E E E ○ E E E E E = J1 η φ 0 Lo ψ η
b ooo η ψ eh - =
E Nl mmouthCJ2CJZCJZ'J2
CJZ blunt += e 工 = え え く え え ：c
:e 工 工Z rA OOth tA 0Oca
caOOcaHOOWca:! : E E
E = = Engineering = =
L) 21 (J 2 rJ 21 CJ 2 CJ
22 L) 20s ωZCJ E E E E E
E E E = E E E − ====)+100
00 t6(/2 ca ttr OOvs ttz
or:c:! : = E E
E-e.

P41 CJ :ll IJ 21 CJ
2 CJ 2 CJ 2 CJ 2
u.

Genus 1 E E E E E E E E = E
E)00(711/3CQtQ00!6(/100)
(/11/1001/Jm52F)215215215
2152152 True (J21 Engineering :E::I::I:
E E E = E E = E E === E
D) I tA 000M 0OOOca
E/l cataOO agony 1 :l: :Ce
E E Work E E E E E
A − = Etn rA 0OOOVc
acacqOOXtaOOE - E E 2: Engineering
Engineering :I::I: E E E E E E -:I
I t12 C/+00f/IMOOO(/JOOOO
Engineering = E
E E Nlro 21:! lmouthZUZυ
2 (JCJ: i!+υ Ward 1 E - E - E E
E = E E - E = :owt/2tAtAo
ocnxooooorawwra.

= I Q = Engineering = E E E = E E = E E
= Engineering = E E = it Ol/l (1)
OO(/l ta OOin ca Oet
E E E S + zua
uzuzzzuzu Dairy industry = = Engineering = E - E゛ = E
E00 l/)OOOOcncatataOOcaX
OOOOe E-E E ===
Engineering EngineeringCJ2tJCJ2LJ2SIJ2C
J2CJ2CJ2 ω A ω =E E E =
E E E E E - E E E = E E =
Work Work lIηcuttAψoOψ閤RoroηXO・=E − E E
ENω black 2+ mouth 2u2CJ2CJZ21 engineering 1-
Engineering = = E E E E
E E E - Reference #1 Shin 4
IL da beak territory -IL ji) (/3f/30001A OC1') 01/10 (
/IOc/)O(/1 'width === E E E E E E E E E = Engineering J2: J21 (J21L
)CJ口UUωQOυωCJQ; Double Q9. A- ,'' Pure Eeeee: C Niseeeeero Eotsumi 2ki, Otsu 2 Otsu 2ki 2 Otsu 2 Otsuki 2ki Z Z :!: :C:C:lnie-z,g
GD, , , .

Erotic L) CJCJL) LIL) (J E E E E E E E E E E E E E E E E E E E: I: :I: :l:
:! : :l: :e 'Ml 20u
2IQ21 Roro L)・c, ttself 工 ：e 、、： え え え え あ
sI x = x x = x engineering =
E Kai Da Da San Shin Da = − t = Ko Meng P,! − Double remainder P === E E 8 Eng
* Masu +1: I OOOOOOOOOOOOOOOOO
= Engineering 1 Engineering = = E - E E E E
E E E U Engineering = Knee F-1+ F4
-1+-P-1-F-11-1+-t F-1, -1=
E E E E E XXX Engineering I/1
ψ = == =EEEEEEEEEE==EE=RO-cl-P400000000000 Cheer affirmation self 2 tomoe 202I tongue 2 self 2□.

cgl E E - E E E - === E - EcoOOm %< 1-1 e-1+-1-+-
I A + F-I F-1+-I P-I F40℃
E - Engineering JL) υυ2 = RI E E E E G100OOOOOOOOOO E E E E E
ENl 21 L) 2 tJ (J:
ll rJ m 2 21 CJ (J Engineering ml Engineering Engineering 2: E E E E - E =
Q EOF4-v4 y4-FI F4-4-1-F4
-F4 EE 2:r: EEEE υuau
zuuauzxauuu Muko = 2: 工 工 え 2: 2: え え え ：C え
E Q E E1111111100MOOMIII1
1111111111111+0OOi-]1;
E xx': g': g E E E E E E - E E E11111 So-Okiichi &l+l bO('11 gN < N l'1 <
1'Q 幇< IN PI (1/111111111
11111+1 Ku Shizuku < Shizuku 4 < Ku Ku Ku Pe Be Ku Be --1111111111110 (/3111
.

1 + + l l l +
I l l I I I
I OtA + −>E E E =
E E E E E E E E E E E E
″: Izeno + + + + +
+ + +QO1/l0Q(1)1
1 1 11 1 1 1
1 1 1 1 1 1 1
1 1 1000c/1= E E ==== E E Work E E =
E E = = Engineering Edition E Engineering Engineering: c: e E E: I: E E E
E E α α cy cy cy α α α α
α O'Aψ to #1 to nku to nku to n go <<<<<<<
o(/l I l l 11 1
1 1 1 1 1 1 1 1
1 1 1000c+2= E E E E E
= E E = E E = Engineering = Engineering = Engineering =
E E E E E
E ml1111I 工 = 匡 ward 匡 2 Sen
x ■ Takashi Ko, 111111111111
11111 α 0 α α cr cy ay
α α α α α α α CYCY α α
- 輌 - Kotono bias! +/ 1. / I+/ V V -li -J
-v v11111111111+1 工 く え
E E E NI CJ ω
Mouth 212 w R E E E E E
- E ==== E E I::l m-1-e-4--tN IN N to NN1111-city+11
111 1:XcyI:yααααααα
E E E E =
= E E =CJCJ(J(JZ2C
JL)口(J(JZZIJ-(JL)11111111
1111+11 Ro 0+AO Roroooomoo
oooo+ao.

1 Engineering = Engineering −= = E E
E E = E E E Quantity -1 E E E E - E :I::E:
Engineering === Engineering Ill E E
E: N2: Eng 2: z:e E -
zz:c = 工１ - え - え
E E E E = Engineering = E
−E E E:l: + t
＋ ＋ ＋ ＋ ＋
＋ ＋ ＋ I II
II + Engineering 1111111111111
111E - E E E E Work E E E E = E E: To C Work - 1 - F4 N40 - NtN ~ Hehe ~ - 1 E
E E E E E
E E E NI CJ 2 Z L)
L) (J CJ (J Z
2 C,) CJ CJ Confucian 100 ro 0 ψ ro 0 ro O
Ro Ro η 0♂l:c ,,:c E
E E E E E E E E 1c, NI l l
l l l l l l l l
l l 1%”I I l l I
I l l l l l l l l l
-E E E E E E = = Engineering = E E CI F4--m m NN
NNN NtN −:I'::l: =
c Engineering = E E E E E
Euuzzuuuuuzzuuuuuzz000000
0000000 VJ wwwcqro 0OOOco
OOOOOOOtaOOOOOO++++++++i
＋＋＋＋＋＋e
E =-+m-+,-1 m-IN IN IN IN
INHEHEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE
E E E :I::I:Nl u
(J CJ (J L) 22 CJ L) (J口ω＝ ″J東：）Jηψηいη4η1■Roro轡：ll Otn OOOO口 ovoo.

＊”l I I I I I I +
□ 1, 1.

♂I l l I l l l l
l l l l Igill"l l
I I I I I
I I I I I
l 頗 = E E E E E E = 工 ：I
: E E : Low-IN N to N('d Nrv-
1-i + E - E - E
- E - = E E = = Z2r, JCJ Roro (J:ImCJCJL
) (J
111111ri lo co η lo o o
O Ro Ro η Ro Ro 0 Ro 0 Ro η 0+111111111111+1black l11
1111+111111111111eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeet
11111111 kudzu 11111111111111Ceeeeee===eeeeee: I:S:C::l::C: Engineering→-1-NN to N IN IN-1-m-1-to = =
E E = Ml (Jω02I2tJω口○(JZ2guess10oooOorAoooRorooNl :e = E E E - E E E
D IC, P -11 Ae Eme Eme Eye Eye = ICGL Works = Ehe Ef Eh (: I P -11-1 -F + 1 + 1
--he NN hehe F-1+-t-P-1l-1-F-1+
-+-1-I P-1-o+ ear ααα ko α αα xx, xx E E = E E =
E E E E uouuuzzuuuuuuzzuu
u■ I l l I l l I I
I I l l l to.

O(/100OOOOZOOro0ro0ηo.

+ I:I: ==:! : :I: = E E = E E E E E -1- E E Z=
=':J:= Engineering = Engineering = = Engineering = II+
1 E E E = = E E = E E - E E E = Sumi1111111'1llllll1
11 + Engineering ===== E E E E E E = E E = E E = Engineering ■ 1 ■ ■ -1111
111= = 1 ■ 1 1
Tomi ■ -111111 k = k = =
E - E E E - = Work === Work Work N
N , -1+-1-++l +p-1m-N to hehe IN
N(N m p-1Nr u L) L) CJ C
J 22 CJ L) L) u u z z u L
l (Jct”l l l I l l
l I l l I I I l l
l l 151 + 1 1 1 1 1
1 1 1 □ 11111, r days + 1
1 1 1 'l l l l l I
l l I l l Engineering 1 Engineering Engineering E E E = E E E E E E E - = Engineering
=l:l-1-I NNN(N NNN-+-+-1-
1-x P4N1 work = E E =
＝ 工 ＝ ＝ 工○口ZZCJ(J(
JC)ω220L)L)0 000011. +
111+100000tlkQOOOOOC1kO=
Engineering = E E E E E - E E E E + l1lIIIll111 ==== E E - = E E E E E
=N NIN 1%de%4 N-111+-1--
～cy cy a cy cr crαααcy c
y(: rα 14th play (continued) Q Yudan R, R, R, R,, R, R.

Q-282H---CI H- Q-2828---CI H- Q-282H---C1) 1. - Q-282H---CI M -Q-282H-
---CI H- Q-282M ---C1)! -Q-11C
HHH---- Q-12CHHH---- Q-71CM --H-Hl (Q-72CH--H-HH QJllCH--)! -H- Q-112CH--8- H- Q-151CI(--C1(l(- Q-152C)l ---CHH-Q-151CH
3---CH3I-1-Q-152CH---C1(l
(-Q-201CM ---SCH3M -Q-202
CH3---SCH3M-Q-2810)(3--
-CI H-Q-2B2C) i3- - - CI
H-8 or 6 ′wi mouse°“ I I l+ o-C
M OCHCM - O-OCI (30CH3CM -O-OCHC) (N -O-DC) (30C) 13M -O-QC)l CI CH-S -0C
R30°H3CH + O-OCHQC)l C1(-O-QC)
[QC) (C) [ HO-OCH0CHC1-1 M O-OCH30CH3CM -OOOCHQC) (CH + OO0CI-10CI(CH -OOQC)I OCHCM - OOOCHQC)I CH-OS 0C
H30CH3CH -OS QC)l OCM C:H-OO
0CI(30CI(3CH -OO0CI(3°cH3CM -O-0CI(0CI(C)1 + o -QC)13 °CH3CM= E
- NIL) (JCJ 212 (JCJ (J
CJ L) Z Z CJ −i″)+ + +
＋ ＋ ■ ■ １ ■ １ ■w”l l
l l l l l l l l
l l l l l lCE;”l x x
E E: E E = Engineering = Engineering = = r1
E E E: E E === E E − =
Work = = = =
Engineering Engineering (: I-x-F-1x--IN to N NN (N
toαα0ααα0αααααcr:ycy= 工=
= Engineering = Engineering = Engineering = Engineering = Ro υ 022 (JL) CJL) LIZ2Ll (J
CJ (Jl 1 1 1 1 1 1
1 1 1 1 1 1 100 works =
E E E E E = = Work = = 11 Work =
= E E = E E E E = Engineering 11 Engineering
= = E E - E E = E - E - =
11111111111.111 = = 工 = E E E E E E E XXZ
xxE E E E - = E E E E E E E E E + -1-111-IN fN IN
to (N (N-m ko α e e e = e
E = = Engineering r-11CJ
Z 2 (JCJ CJU (
J Z Z L) L) Ll [
J L) Z] E) I OOOOOOOOOOOO
OOOOOOO)l OOOOCfl OOOOO
OC7) OOOO-1E E E E E E E E E E E E , 1.1♂l l l
l l l l l l + l l
l l l l l knee 1 1 1 1
1 1 1 1 1 1 1 1 1 1 1 1 1
Engineering 1 E E E E E = E E E E E = = E E -C
HI F-1-x l-1+-+ IN IN IN
IN N(N N++1-P-I F-1E
E E E E E E E
EZLI(J(JLIL)ZZL)CJLI(J(J
2Z0000000000VMcncnH Engineering ==== E E E E = = E E E Engineering = E E E E = E
E = E E E =+-t +-+ 1-17N
(N IN NNN (NP-11-I P-I P
-I F-1E - E E E = Engineering = = Engineering? JI CJ (,) CJJL) Z2C
J(J(JRoro2-i"z5>+ t/1 tA xxwcnxcntaoo
o.

″)1.
ro η o o ro 0*”l l
I l l l I I l l l l
l l l♂l l l l l
l l l l l l l l l 1
,''''I I l l l I l
l I I I I I I I -
= Engineering = Engineering = Engineering = E E E = Ro-4
N NIN〜〜〜〜１１１１ え−え ＝ え え ー え Ｇ ＝
E E =Z(J(J(J RO UZ
ZU ro ω (J(J2Z(JL)(Jri o
o lo lo o o o o o
I I I I I I I
I coot Ao Roro 0 Ro oc110 Rororo 0 Roη Ro, insect 11111111111111 ==Eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee
NIN NN4N To N--m-,-1--HeRRR Q-282M --- Q''''11 °83 HH- Q-12CM HH- Q-710)t --H Q-72CH--H Q-111CH--1 (Q-112CM --H Q-151C) (--- Q-152CM --- Q-151CM --- Q-152CM --- Q-201CH, --- Q-2020M3-- Q-281CM --- Q-2820M3 ″''] Table 5 ( continuation) (:I M --0-CI(30CH3CMC1
)(--0-0c1(0CI(C)1CIH-
-0-OCHCM NC1)l --0-0C
H30CH3NCI H--0-0CI-I
CI CHCI H--S -OCHOC
HCH---0-OCHOCHCH---0-QC)(QC)l CM-
)(H)IO-QC)(QC)4 CM-
HHHO-OCHOCMC)1-H
--000CHOCRCH+ H+ +
OOOCHOCHCHCHHH--00QC) (0C
I (CH CM ) (--00QC) (OCH0MCH3M
--OS OCH30CR3C) (CM
H--OS DC)l OCRCHSCHH-
-000CH30CH3CHSr1 (3M --00
0CH3°C1-C1-13CH--0-QC) (OC
HCM CI M --0-OCHOCHCMli
111 bar (,1() (J (J U
l (j u Lme (me (me:!:= 工 = 工 ==== 工 :):!:e:e:e:e
:l::eZCJ ri Q υ CJCJCJ(J(
JCJCJCJ (JCJCJCJCJ Re Q:e
:! : 0: Work = Work = Work ====
E: e: c: e: e: e=c″′ = 工 = :c 工 工 ：[(J:!::!:
E E E = 工 === 工0OoooOoO0
00oooooooo mouth.

E E = Engineering = Engineering = E E E E = Engineering Ml (J LI C
J LI CJ L) CJ (J CJ L) tJ
(J CJ CJ E-E E E-E
= Engineering === Engineering === Engineering υ(JL)υ
uuuuωuuuuυroωro0 工 = E E
E E E E E E E E
E E Work E E E E E E
E - Work E E E E E E E E === 工oooooooooo
ooo b ooo.

= E − E Erotic 0
b 2 b
2 u = engineering engineering = engineering
=== Engineering Engineering = Engineering
===o oo o
Ro O.

, 1 Waka Tomoe Tomoe Self Self Self Tomoe Tomoe Tomoe Tomoe Ni E E = 工 ：I: ：e ＝：e ：
e :e :e 工 x==':r:==koωu
uuuω○Q Roroω0ω mouth (JCJ mouth○=== E
E ==== E E E E E = E E E == E E E === Engineering = Engineering = =
E ==== 工m-m-1-1--m m +
-+-1-1 ++1-++1 +-I F-1''.

= d m F4 P-I P-1-F-1-1-4--F
-I P-I P-I P-1+-+1+4--F-I
F4 +-1-I P-1-F-I F-I F-1
1-11-11-I P-1= 口= Mr. 1 E E E E E E = = E E ==
= Engineering = (:I l-1-P-I F-1x l-
IF-1-1-IF-11-1gs M-m AE - x xr: xx
x222(,)(JCJ(J(J CJ(J2(
J (J
em P4 -+4--F-I M machining 1 E
E E E
E E E CIF-1--s 1-I
F-1x engineering = =
Engineering == E
E E -F
-1++I m-++1 工」L Q46 (R,・R13□M) Q-50 (R, R-H) Q-53 (R15 wealth H) Q-59 (R厘H) Q-61 (R , R dew CH) Q-46 (R, R Explosion H) Q-55 (RsH> Q-37 (RgH>
R work 2, R13, R14”H) Q-72 (R, RxH,
n'rl) Q-78 (R engineering 2, R-, 3, H) Q-52 (R, R wing CH, R snow H) 12 >4 313 R H H H 28H0CH30CH3CH 28HQC)l OCHCH2880CH
OCHN 2 H80CHOCHN 2)IOC)l QC)! N2
H1(OCHOCI'4 N21(MOCHQC)I N2M
)4 0CHC)(N 2)IHOCHOCHN 0)1 H0CI(OCH)J 190-193
E: I: Ei Ei: I: Ei Etsui: E -O -Omiko.
E:! : E E E E E
-Roooooooooooooooo.

(Me 01 C) Lν (, l (j (
j Lν
== Engineering = E E E E = =000000
00 +-1-r-a F-1-:) U (JC)
() (J (J () (J (,1(j (J
LJ3 and Q-59 (R stock H) Q-62 (R12 “H-R13” CH3: Q-66 (R
12, R13, R14″H: Q-78 (R12/R13
“H) Q-53(R15”CH3) Q-72(R,R-I(,n'-1) Q-69(R12・R13”H) Q-46(R,R-H) Q-49 (R12・R13"H) 0 table (continued) Melting point n REl xl ('C)l
HHOCH.

l　HH0CFH 1HHOCH.

L HH0CH3 2HHCH.

2 HH0CH3 2HH0CH3 2HHCH3 2HHOCR (J () C) 01010I C) 0
101 Cn () () ==== E E = Engineering = E E E -= E E E E = Engineering =
Engineering = = Engineering Engineering oOOooOOOO〇-11- Oυ C) :!::!! E E E :l1l
j:e:e:! :! :! l::l:NI LI C
J CJ CJ CJ (J (J
(J (J CJ CJ CJ U=
= Engineering :I::! :! :! l::L: 工! :!
::I::e:! : 工 -=uuuuuuuuu
○ (JCJCJ(J ○ 0 υ:!::!::
! ::! ::! ::! ::! ::i: 工 ===
Engineering ====:e″′ Engineering :c :!: u:!: z:* Engineering :!:
= 工 工 z:cz:e:coooooooooooo
ooooooo.

= υ :I::! :e:! ::! ： 工＝＝ え え
E = =t-al C,) CJ CJ (J CJ
CJ CJ (Jrishiku JC, +CJ= Nie E
E = = Engineering =:! : E E E E= 工
Engineering =E:e:e:! : :e:e:*:e 工 =
=E E ==Technical varnish=o o o o Oo o O
OOOo o o oo o.

0 0 C) C) () CJ (J
u (J u (J (J 1zzz)
zzzzzzzzzzzzzzzzu 工 === 工 =ez:c:zr::c え − = 工 = −
= 工 x: r: xxx'x, x = xx”x:
= xx'r: xoooooooooooooooo
o.

) OC) C;I C)(J OIJ (J (J
(J (J (J u LJ enemy1..lu +,,
m e − e e === e e =31 u u 2 2 2 (J
(J U U (J (J U U C
:I OOOOOOOOOOQ OOO0work = E
E E E E E E - E E E E E =
e:1: :c= E E E E E E E E
E E E E E E E E = elo
O00000000 [(j u
C)C)C)Cn (y O(n)
(c:e:e=
= :! :JCJC,
) (JZ C,l
Z uichiro e = = engineering
======= Engineering ===nu
0 (,IC) (,
l L) ・---= Engineering
= :0 工 :r: = E − = ;U ○
CJCJ (J υ ○ υ OQ (工 Z!: e:
c:! : :! ： ：c：e ゝえ ころ え ：Il
::r::r: E E − = E − E : e
Z:! : :e :JCJ(J(J(J(
, l ○ uuuuuuuuuu: :r, 工
:I: E ==== Engineering :c:e:e:e
:cr:峨-111111111111工二:! ::! : Engineering = Engineering = Varnish Q Q ○ (JCJCJ(J(J= = E −
E = E E = === Engineering -= = Engineering = -1r-4F-1p-4+-I F-1-11:! ::
! : (JCJ = engineering xx = xr, engineering ==== engineering
:c = :c=:exxxxxx 工 :e =
:r:ezz E - ====--1-11-1
1-1+-4m s-I P-1+-1? -11-F
-1-1〒 :! l::! ::! ::! : Engineering = Nl (J
(, l u u CJ u z z
z z z z z−′ de:l::! l! :e:e:! ::e
Engineering =zzzzzzzzuuuuuO
:' :e:e:e 工 === え え === υ
=== E N-+, -11-I F-1
, -1-Me1-I F-1+-1+-11-I P4
F-1-1s engineering: (I l-11-11-11-11-11-1rs +
1-11-I F-1= = ==, ω Loss 2 L) u , = = E E = E E E x = xx
= Engineering =C:I-x x
l-11-1-1 = =
Engineering = Engineering = Engineering = u
(J Z (J ○ υ ○口QOe
E E E E E = E E E E E
E === E E =+ +
+-t e-t ---
He He He ==== Engineering F41 C) m 2 :I: 2 2 2
2 (J (J (J CJ 2 2 2= 2l N f”J N ('14 (%4 to
= = Engineering ω
z CJ C)
υ 2 engineering = =
E E − 工 E= 工 ：e :c：e：c え え :! :=
E E E - E E E E = Engineering:! ::C:
l::Ce Ee =00000000000 Roro 0 ==Eng:! :r::m:e:e=:r::! :e! ! :
1:G Engineering=0: Demand:e:z:e Engineering== Engineering= Engineering==
Eng.
12 wings H-R13 woven CH3) Q-78 (R12/R work 3
-H) Q-53 (R15''CH3) Q-72 (R12, R13=H, n', 0) Q-73 (
R, R-H, n'-1) Q-46 (R, R, H) Q-49 (R12/R13, H) Table 17c (] Melting point n REl xl ("C)L
E()I 0C)t3 L HH0CFH 1HH0CH3 L )I )I 0C)I.

2 HHCH3 28H0CH3 2) I H0CH3 2HHCH.

2 8 HQC2H5 = E E E E E E = E E E E E E E = xxxx E E = E E E E E E E E OOOOOOOOOOO1-1-?
r-a P-I P-IC) 0f() C) (j
C) (J (J CJυUsuJQUe
E E E ==== E E = Engineering :r:=
Engineering = E E ': r, Z: r: ZZ E E E E = = E E E =000000000
00 M, -+ 1-1, -11-1 x F-1o
ooooooooot;ooo6o6otf>-Ω- Q″″61(R12=H,R13″C)I3)Q-72
(R, R, H) Q-78 (R work 2. R work, -H) Q-46 (R work 2・'13"H) Q-53 (R15"C) I3) Table 17e (down) l HHC) I3CH3 1) I) ICHCH col HHC) I3CH3 2HHC) (3CH3 2HHOCHCH 2HHC) I3CH3 2HHOCHC) ICF.

E E E E = Engineering E === Engineering E ===
Work = = Work = Varnish work E - = Work = Work 00
00ooo0000-111" Q-55 (R, °CH,) Q-59 (R dew H) Q-61 (R12"H-R13"CH) Q-63 (R
12”H, R13,, CH3) Q-72(R,, R13
"H"°"O) Q""83 (R12・R13-H) Q-46 (R, R Dew H) Q-53 (R15 wing CH3) Table 17j (continued) EX Melting point n Rl 3 (℃) l
HHCH.

l HHCH3 1HHOCH 1HHQC) I3 2 H) (0CH3 2HHOCH ko:,) H Sea・(11 people I's transformation −゛・η useful 1・′; 1 =;′41
: J is calculated by Karizune's method "ψ)1i'j L. Those i
"t, + boyfriend fi, book j・kawa, ↓ foot i'T'L % turbidity 1
C1l, hole path, hydration dorsal i11. ',! Thick breasts: 1 etc. It can be used directly 15' times for many things.

1.Tshi...;Use...;H,J c used. Is the 3rd strong role So Naruki an intermediate student J shaku j for later synthesis? It is mainly used as 1. To summarize, it is 1! The active ingredient is approximately 0.1~
99110i: ', 'o, and a) Rokumen Qing 1 King is 1
Bot 0.1 to 208 and b) Solid or ge body fan/shaku 11
The preparation will contain these components in approximately the proportions shown below.

+
；も
ψ ~ + Stone ★ 441 Of course, it is lower than the table or S, ;") u: a's t ancient note j attack 5 Sum also depends on the intended use and the physical properties of the compound.Surface activity A high proportion of the active ingredient V is particularly desirable.
L<,' is achieved by incorporation into the preparation or by mixing in a tank.

A typical solid diluent is Watkins
“Handbook of In5ecti”
cideDttst Diluents cLnd
Carriers”, 2nd edition, Trandobu 7ri 7,
Company (Dorland Books.

Caldwell, N. J.), but other solids, both natural and synthetic, may also be used.

For hydration-reducing concentrated powders, adsorbent diluents are also suitable. Typical liquid diluents and bath agents include Marsde 7 (
Afarsden), “5olvents g.
uide', flute 2nd edition, Interscience Co., Ltd.
ersience.

#,]',), 1950 KM myself! Saletail. 0.
A solubility of 1° or less is suitable for D-thick suspension milling; thick α
The cut is preferably stable relative to the phase fraction MY at O'C.
Ann
1Lal”, Alarerad Publishing Company (, 1lured
publ, corp.

N, Y, l, and VC7 5isely and Food i,” Encyclopedia
ofSurlace Active Agents
”, Chemical publ
, Co, Inc.

N, Y.), 1964, displays surface activity and its recommended uses. All formulations may contain small amounts of additives to reduce foaming, caking, corrosion, microbial growth, etc.

Methods for producing such compositions are well known.

Solutions are prepared by simply mixing the components.

Finely pure solid compositions are prepared by mixing and commonly grinding using a hammer mill or fluid energy mill. Suspensions are made by wet milling (see Littr, US Pat. No. 3,060,084). Granules and tablets may be prepared by spraying the active substance onto preformed granular carriers or by agglomeration methods. References J.E. Browning, "Agglomerat"
ion @, Chemical Engineeri7L
g, December 4 issue, 147 negative (1967), and Berry [PCrt”V) M, Chemical Engi7
Lee's IfL: Lndbook, Part 5'r
:L, + Tsukugu Ou Hill Co., Ltd. (5fcGrcLw-IJ
i 11.

N, 5', ), 1973, pp. 8-37.

In the following examples, all copies are by weight (unless bf).

g: ff5I9li 12 Water agent/v-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-(inxacilyl-6-yl)-2-thiophenesulfonamide 80% alkylnaphthalene sulfone Sodium 2% lignin sulfone r: disodium 2% synthetic product 'B,'/υ force 3% kaolinite 13% above rJ
Heat for 20 minutes and crush with a hammer mill to reduce the average particle size to 50
Below the gokukon (strain, iJ, mixed and packaged.

Actual θm Example 13 Irrigation agent 3-(Ink length Sol-5-yl)-N-[(4-methoxy-6-methyl-pyrimidin-2-yl)-aminocarbonyl)-2-thiophenesulfonamide 50% Alkylnaphthalenesulfone Sodium 2% Low Viscosity Methyl Cellulose 2% Keinke 46% The above ingredients were mixed and coarsely ground in a hammer mill and then ground in a Shinki mill to produce essentially all of the particles less than 10 microns in diameter. This homogeneity was remixed and packaged.

14. Irrigation agent of 15. 5% athano-ξrugite particles (US standard sieve No. 20-40 HD,
84~D, 42 r, a) 95% solids 2
A slurry of water-friendly powder containing 5% was latched onto the surface of the atta/zourgite particles in a double cone mixer. The particles were dried and packaged.

Example 15 Extruded tablet N-[(4,6-dimethoxybilylξ din-2-yl)aminocarbonyl]-6-(inxacilyl-3-yl)-2-thiophenesulfonamide 25% anhydrous sodium sulfate 10 % crude calcium lignin sulfonate 5% sodium alkylnaphthalene sulfonate 1% calcium/magnesium bentonite 59% The above ingredients were sweetened, hammer milled, and then moistened with approximately 12% water. This mixture was extruded into cylinders approximately 6 mm in diameter, and the cylinders were cut into tablets with a length of 5 v.*.

Can it be used directly after drying? ″
ii) The dried C tablets were crushed using a US (Q$ Fluid No. 20 (opening 0.84 rw)) V [(eggplant).

US standard sieve No. 40 (opening 0, 42 wijI) V
C-The particles that remained were packaged for use and the bottom of the sieve was circulated.

Example 16 Low strength granules N-C<4.6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-(inxacilyl-3-yl)-2-thiophenesulfonamide 0.1% atanozo Lugate particles (US standard sieve 20-40 mesh) 99.9% active ingredient was dissolved in a solvent and the solution was sprayed with dedusting particles VC in a double cone mixer. After the solution jet 6 was completed, the material was warmed to evaporate the solvent. The material was allowed to cool and then packaged.

Practical example 17 Granules 3-(isoxazol-3-yl)-A'-[(4-methoxy/-6-methyl-bilyzine-2
-yl)-aminocarbonyl) -2-f offenesulfonamide

80% wetting agent
1%tL E lignin sulfone = + salt (5-
2% natural sugar content) 10% atta zhorrugite clay 9% The above formulations were mixed and ground and passed through a 100 mesh screen. This material was then added in a fluidized bed granulation manner, the air stream was turned off to gently fluidize the material, and a fine jet of water was sprayed onto the fluidized material. . Desired size: 1. σI until the surrounding particles are produced
1. He continued to animate and bite.

Although the spraying was stopped, the water-containing fireflies were -V2. (I was able to sell both while heating the fluidization until it was reduced to the desired water fist with τ1% or less.) Next, I took out this i'7J quality and passed it through a 1 ton sieve to obtain 14-100 mesh (1410-
149 microns) and packaged for use.

Example 18 Low strength granules N-Cl4.6-cymethoxypyrimidin-2-yl)aminocarbonyl]-5-(inxacy-5-yl)-2-thiophenesulfonamide 1%N,N
- Dimeterformade 9% attapulgide particles (US Standard Sieve No. 20-40) 6% dissolved in 90% 0% active solvent and the solution sprayed onto the dedusted particles in a double-cone mixer. After the solution injection was completed (but the mixer was left running for a short period of time, the granules were then packaged).

Example 19 Aqueous suspension N-Cl4.6-dimetherpyrimidin-2-yl)aminocarbonyl]-3-isoxazol-3-yl)-2-thiophenesulfonamide 40% polyacrylic acid thickener 0.3% dode /Lphenol polyethylene glycol ether 05% disodium phosphate 1% phosphorus
Sodium 0.5% Polyvinyl alcohol 1.0% Water
56.7% The above ingredients were mixed and ground together in a sand mill to produce particles with essentially all dimensions less than 5 microns.

Examples 20 Bath liquid 3-(inxacil-3-yl)-A'-[(4-methoquino-6-meterubirimidine-2
-yl)-aminocarbonyl i2-thiophenesulfonamide, sodium salt
5% water
The 95% term is watered down τI! '：Press it ILL
In addition, in June: y to manufacture and use it next time.
ζ packaged.

Example 21 High strength thickener N-[(4,6-cymethoxypyrimidin-2-yl)aminocarbonyl]-3-(inxacy-3-yl)-2-thiophenesulfonamide 99% silica airgel α5% Synthetic amorphous finely divided silica 0.5% The above ingredients were mixed and ground in a hammer mill to produce a highly thickened agent that essentially all passed through a No. 50 US standard sieve (0.3 m opening). . This material was then used in various ways to produce preparations.

22 Irrigation agent N-[(4,6-dimetherpyrimidin-2-yl)aminocarbonyl]-5-(inxacilyl-3-yl)-2-thiophenesulfonamide 90% Sodium sulfone dioctyl succinate 0 .1% synthetic imitation silica 99% of the above ingredients? iA
The particles were combined and ground in a Shimmer mill to produce particles essentially all of which were less than 100 microns. This material was passed through a No. 50 US semi-sieve screen and then packaged.

%, >”atl 23 Hydrated 3-(inxacy-3-yl)-N-CI4-methoxy-6-methyl-pyrimidin-2-yl)-aminocarbonyl]-2-thiophenesulfo/amide
40% ricin sulfone! +2 Natoriwam 20% Montmorillonite (Mountain Earth)
40% of the above ingredients were mixed thoroughly to 2J L/L, crushed to +L16J in a hammer mill, and 1YF in a VC nitrogen atmosphere.
61・r-wise, all the dimensions were 10ξchron.''Buto's king, S-ko, was made one or two times, and seven paths were created. I mixed this 1 7 ゛ [, r large (ζ し (shi).

'7', i:, +:124 N01 sex! Si1, iQ? i'1 N-CI4.6-Simethoxypyridin-2-yl)aminocarbonyl]-3-(inxacy-3-yl)-2-thiophenesulfonamide 35% polyalcohol carbon in Tennis chill solution and dissolved in raw Petroleum sulfonate mixture
6% xylene
59% The above ingredients were combined and ground together in a sand mill to produce particles essentially all of 5 Vicron or less. The product can be used directly, bulked up with water or emulsified with water.

Example 25 V) Agent A'-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-5-(inoxazol-5-yl)-2-theophenosulfonamide 10% athanozurgate 10 % pyrophyllite 80% active ingredient was mixed with attapulgide and then passed through a no-shimmer mill to produce particles substantially all of which were 20 microns or less.

Approximately 0 to 1 part of the pulverized material was then mixed with powdered pyrophyllite until it was evenly distributed.

26 Oil-based 5-(inxasil-5-yl)-N-[(4-methoxy-6-methyl-pyrimidin-2-yl)-aminocarbonyl)-2-thiophenesulfone Amide 25% polyoxy/ethylene rubitol hexaoleate 5% 1'
, fat, carbonated water 7;] oil 70
% of the above ingredients in a sand mill (crush)
The solid particles were chopped to a size of about 5 i chrome or less. Crossed over:
It is best to wash it with oil for 1-1 minutes or in water.

Fruit 1.te512li 27 Wettable powder A'-[(4,6-dimethoxy7bilimin-2-yl)
Aminocarbonyl]-3-(isoxazol-3-yl)-2-thiophenesulfonamide 2
0% sodium alkylnaphthalene sulfonate 4% sodium likunin sulfonate 4% low viscosity i-methyl-t: # I: l-s 5% athanorugite
69% of the above components were fully combined. Milled in a hammer mill to produce particles essentially all below 100 microns, the material was remixed, passed through a No. 50 US standard sieve (0.311 aperture), and packaged.

Example 28 Wettable powder N-[(4-chloro-6-medoxypyrimidin-2-yl)aminocarbonyl)-3-(1#-pyrrol-1-yl)-2-thiophenesulfonamide 80% alkyl naphtha Vsulho/i,,1. “-i-to’J kum
20 lignin sulfone 1st wave sodium 2° lignin sulfone shaped silica 3% strength
Mix 15% of the above ingredients, grind in a thermometer mill at 1 so that all solids have an essential VC of 50 microns or less, and re-mill. j-A and packaged.

Harm: 1 case 29 To irrigation 11 N-C<4, b-dimethoxy/-1,5,5-triazi/-2-yl) ゛aminocarbonyl]-5-(1tt-
pyrrol-1-yl)-2-thiophenesulfonamide 50% alkyl≠phthalenesulpobe, manodium
2% Low J Fortune 1p-Megur-Hirloth 2% Kei-no-shi
46% of the above ingredients were coarsely ground in a hammer mill and then in a Seiden mill to produce particles essentially all of which were less than 10 microns in diameter. This material was remixed, And packaged.

Example 30 Extruded tablet /V-[(4,6-dimether-1.3゜5-triazin-2-yl)aminocarbonyl:] -3-(I II-pyrrol-1-yl)-2-thiophene Sulfonamide 25% anhydrous sodium sulfate 10% crude calcium sulfonate 5% sodium alkylnaphthalene sulfonate 1% calcium/magnesium bentonite 59% The above ingredients were mixed and ground in a no-mer mill, and then about 12% moistened with water. The mixture was extruded into a cylindrical shape of about 3 tt, which was cut into an islet about 5 B in length. These can be used directly after drying or passed through a US standard sieve No. 20 (0, 84 vx).
7. There was nothing to do.

Rice (4HJ f!''-'rlJ = Sieve No. 40 (openings 0)
．． 42 = z) to use the particle that straddles a1) and 11 [・This is also impregnated and n'(;'III was made by clever circulation.

NatsuzokatiiiyiJ31 1 1'(RIτ, ILF τbz;乍) NOV-[(4,6-dimethylbilidin-2-yl)aminocarbonyl]-5-(INKISA-3-YL)-2 Thiophenesulfone Amide 0.1% atta/zhorgite particles (wood h, grain, -: semi-sieve 20-40
Mesonyu) 99.9% ``Ultra 1'Il''
: You lost the game in 411 games, and now you're invading Double Cone? Particles leaving the D ridge Cte l・lj '; fT L
/Ta. After the spraying of the mash is completed, warm up the substance and heat it.
I set him on fire. Cool the object/page by exposing it to Ir11? ;
(: 17 was packaged.

1r, row 91 32 Author Ha'? A'-[(4,6-dimethoxy7pyrimidin-2-yl)aminocarbonyl]-3-+1#-pyrrol-1-yl)-2-thiophenesulfonamide 80% wetting agent 1% crude
Sulfone r9 salt (5-2C 1% natural content)
10% Adanosorgite clay
9% of the above ingredients were blended, ground and passed through a 100-men 7-U screen. The material was then added to a fluidized bed granulator, the nitrogen flow was adjusted to gently de-energize the material, and a simulated spray of water was sprayed onto the fluidized material. Fluidization and atomization continued until particles of the desired size range were produced. Spraying was stopped, but the fluidization was continued with optional heating until the water content was reduced to the desired water LV, typically less than 1%. This material was then removed, sieved to the desired size range, generally 14-100 mesh (J 4 J O-149 microns), and packaged for use.

Cannon Example 33 Low strength granules N-[(II-methoxy/-6-methyl-1,5,s-triazino-2-yl) aminocarbonyl) -3-< T n-pyrrole-1
-yl)-2-thioquenesulfonamide 1% iV
, N-dimethylformagode 9% attapulchite particles (Kishi 821 standard sieve 20-40 sieve) Dissolve 90% active ingredient in solvent, then double cone, kongo hekko and 1 bath
The town was attacked by IQ particles. Common, Kei no Te (H-q Gau 6
After finishing, VC also drove Mixed Legend +IIJ for a while,
Next, the VC particles were packaged.

Child j= j;:r4i/II s 4 Permanent residence Ml
'h) I iL'L N-[(4-methquin-6-, methylbilimicin-2-
yl)aminocarbonyl)-3-([/-pyrrol-1-yl)-2-thioquenesulfonamide 40% Polyacrylic-2 Sosocner 0.5% Dodenlephenol: i? Liechele/Glycol ether
. , 5% phosphorus a disodium
1% sodium sulfate
0.5% polyvinyl alcohol
1.0% water
56.7% The above ingredients were mixed and ground together in a sand mill to produce particles with essentially all dimensions less than or equal to 5i microns.

Example 35 Solution 3-(5-Chloro-IB-1,2,4-triazol-1-yl)-N- [(4,6-cymethoxybiliξdin-2-yl)aminocarbonylcy2-thiophenesulfonamide, Sodium salt 5.
! a water
Add 95% salt to water while stirring to prepare a bath, which is then used for 1'? -Packaged.

-;, qu+J 36 Suiga0he11 N-C<4.6-diphtoquinbyrimidin-2-yl)ami7carbonyl]-2-(1#-1,2,4-)lyazol-1-yl )-6-z lysine sulfonate 80% alkylnaphthalene sulfonic acid) IJum
2% lignin sulfone anodium 2% synthetic non-rectangular silica
3% kaolinite
13% The above ingredients were thoroughly mixed and ground in a thermal or mechanical mill to produce particles having an average diameter of 20 microns or less. This material was remixed and packaged.

Tenba'1fe114+1 7 Shikako Shino tarjro p is - N-[(4,6-nonotoquinbiliminon-2-yl)ami7carbonyl l-2-(I H-1,2,4- Triazol-]-yl)-3-pyrinonesulfone 7mide
5.0% mixture of oil-soluble sulfonates and polyoxyethylene ethers
4.0% N-methylpyrrolidone 4
5.5% xylene 45.5%
The active ingredients were combined and stirred until dissolved. A fine screen filter was included in the packaging process to ensure that no other undissolved M material was present in the product.

The compounds of the present invention are powerful herbicides. They are used in areas where complete removal of all vegetation is expected, e.g. fuel storage a.
Around tanks, around ammunition fi, industrial storage area, ITt
Widely used for extermination before and/or after germination of miscellaneous in fields, outdoor theaters, around billboards, highways and railway areas!
Indicating the usefulness of fl, the present compounds can be used to eliminate weeds in crops, particularly wheat, barley and soybean, before and/or after emergence! It is also useful for selective extermination after J.

The rate of use of the compounds of the invention will depend on the use as selective or systemic herbicides, the coexisting crop species, the weed species to be controlled, the weather and climate, the formulation chosen, the method of application, the vegetable crops present. Determined by many factors including: Generally speaking, the compound should be used at about 0.01 to Skg/ha.

In this case, light soils and/or low content n'! ! Low currents in the above range are used when applied to soils with a high J quality content, when selectively removing dirt, or when short-term sustainability is the only consideration.

The compounds of the present invention can also be used in combination with commercial herbicides of the pond type, such as triazines, triazoles, hexaranyl, urea, amides, nophenyl ethers, carbamates and bicarbonate-linoleum type herbicides.

The compounds can also be used in combination with mefluinode.

The herbicidal properties of this compound have been demonstrated in a number of greenhouse tests. The trial method and lf conclusion are as follows.

Human milk and crabgrass (Digitaria =, n, ), golden millet (Echinocl+Ioa crusgmll)
i), Oat (Aventtfreui), Ebisugusa (Cassia toral, 7sio(1pos)
oeaSO,), Onamomi (X antl+iu*
sp, )% Sorghum/maize, soybean, rice, and wheat are planted with tubers of hamamata in the growth medium,
Pre-emergence treatments were carried out using chemicals dissolved in solvents that were harmless to the plants. At the same time, these crops and weed-like species were treated with the soil 7-leaf application method. The height of the plants was 2-18 cm at the time of treatment.

Keeping the treated plants and the N-light plants in a hotbed for 16 days,
All scales were then compared to controls and visually assessed for response to treatment. The evaluation method used was based on a scale ranging from 0 (no effect) to 10 (maximum effect). The following letter symbols have the following meanings.

C: Yellowing or! 1lli destruction; G = ecstasy delay; H = shadow formation effect; U = abnormal pigmentation.

The compounds were highly active herbicides. Wheat has shown resistance.

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7.
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n Shinki, Ki Muroksune table A (continued) Compound 89 Usage rate 9/ha 2000
400 Meta 1-β- λ Summer- 2 round pots (525cm x ffj) 22.5c
Filled with woodstone sand loam. Black glass in one pot (A 1 opaeuruz Bos
uroidcs), Guikon, Cyperu
s roLundus), crabgrass (D 1g1La
ria znBuinalis), Cassi
a obtusifolia), TearaiS id
A 5 pinosa), Chi 5 Sen morning glory (Das
Lrimo mouth 1u-), Berberatori-7
(A butilo .=ophrasL i ) and P. phragma (Setar3bc+rii). Wheat, cotton, sorghum, soybeans, oats (Avcna f,
um prozylvnnicus), talent (I po
aori hedcracc*), ditanning 5o
rH1+us I+alppr+r+Sc) and choa erasHalli were allowed to grow for about 14 days, and then sprayed after germination with the dissolved material in a non-phytonutrient solvent.

2 round pots (i7T (fi25ca+Xff312.
5cm) with a hooded tone sandy loam soil. 1
Black grass (A Iopaeurus) in individual pots
Bosuroid5).

I planted sugarcane fern, /) 7 Japanese centipede, / ashba, sicklebod, teaweed, Chinese morning glory, velvet tree 7, and psyllium/frogweed. In other pots, we planted wheat, cotton, rice, corn, soybeans, oats, Japanese fir, morning glory, zitanson grass, and snail grass. 2gA pans were sprayed with chemicals dissolved in a non-phytotoxic solvent prior to germination.

The treated plants and controls were kept in the greenhouse for 28 days, then all treated plants were compared to the controls and tested! Plant responses were evaluated visually using the evaluation method described for 2A. The data are shown in Table B.

Ji! It has been certified.

Arrow K ka yahe 8 + HK K ”b -ka 1, -t
to aooaaaaooooaooavoooa
Q) +/l small N~ (F QO
LIC5(jOc5c500(joOGQo(50O1
to0OOcQd1 r'lo >J $NCh
-H-- Seven K or p to 3 II-
Vbe pefu 1bu beast poverty, -1000 (jQQOOOOOOOOOOoOOC5-
ω small n seven be or dice eight sak
h fu force 1o o a CJ a
[50,000 unitsooaoaoa.

1'QN('QX M N
N N-ri↑ma ni kazome he 8 kobemu) 1 knee! -shi (Kuji 2r11's Borie Senshinliner fJ Sano Plasti/Rina Veninia 7ζi ko・! Shita Sasa 7u':, 610-mu soil light tilt 12, 141-i Benikol tI?″TT
rilic++m nes+ivum), enter 1 (I
I ordrun vulBXIrr), empty wheat ()\vena1'nLul3), cheat gelas (Imi1' o m U S °+rralinur,),
Pla°/Kugrus (8loI+rcuru= 111
yo'1llrclI/I(''S), -Year 11, Bluegra'l (I'on annun), Green 7 Oxtail (S eLnria viridi
s), Italian Lygramata ([-olius m
ulLiflorum) and loop seeds (Dras
=ia napu<) II'f was obtained by hQ. earth pot;
ali), Creepers (Gallium npnr
inr), λ beadwell (V Cronieapcr
Sien), Fuchia (Kocl+in *copar
ia), neffer super measure (C, np:=+ll
n bursn -na<Lorie,), matricaria i/de
La (MaLrienria 1nodora), black nightshade (Solanumniqrum)
, Wild Book Wheat (PolyHonu+er
onvolvulus) and satwadaif/(BeL
In order to inhibit a vu16ari*l, the above two pots were treated before germination. Same H, r i ko'', t of the note
2 pans with 2 blades of type 1 and 10H - 71
What is the height of the plants after the two treatments? It was 112 cm depending on the elongation order of the +7T object.

Compound No. 3 was diluted with a non-phytotoxic solvent and sprayed onto the top of the pan. Untreated control and solvent only control m
For comparison purposes, all treatments were kept in a greenhouse for 2:7 t.] 5) The treatments were compared with the control in a cage kept open for -22 days, and the effects were visually evaluated. The recorded data is shown in Table C.

Compound No. 3 had high herbicide activity at non-limb application rates on wheat and barley. .

Claims (1)

[Claims] 1. Formula ¥Ia¥, ¥Ib¥, ¥Ic¥, ¥Id¥, or ¥Ie¥ ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Ia¥ ▲There are mathematical formulas, chemical formulas, tables, etc. ▼\Ib\ ▲There are mathematical formulas, chemical formulas, tables, etc.▼\Ic\ ▲There are mathematical formulas, chemical formulas, tables, etc.▼\Id\ ▲There are mathematical formulas, chemical formulas, tables, etc.▼\Ie\ [In the formula, R is H or CH_3, n is 0, 1 or 2, w is O or S, and Q is a phenyl ring or a saturated ring containing one heteroatom selected from sulfur, oxygen or nitrogen. unsaturated 5- or 6-membered rings or containing 1-3 heteroatoms selected from 0-1 sulfur, 0-1 oxygen or 0-3 nitrogen; or a 6-membered ring; in compounds of formula Ia-Ic, Q is optionally SH, C
_1-C_4 alkyl, C_3-C_4 alkenyl, C
_1-C_3 haloalkyl, halogen, C_1-C_3
Alkoxy, C_1-C_4 alkylthio, C_3-C
_4 alkenylthio, C_3-C_4 alkenyloxy, C_1-C_2 haloalkoxy, C_1-C_2 haloalkylthio, C_3-C_4 alkynylthio, C_1
optionally substituted by one or more groups selected from -C_4cyanoalkylthio, C_1-C_2alkoxycarbonylmethylthio or C_1-C_2alkylcarbonylmethylthio, and in compounds of formula Id and Ie Q is optionally C_1-C_4alkyl , halogen, C_3-C_4 alkenyl, C_1-C_3 alkoxy, C_1-C_3
Alkylthio, C_3-C_4 alkenylthio, C_1
-C_2 haloalkoxy or C_1-C_2 haloalkylthio, E is H, C_1-C_2 alkyl, C_1-C_2 alkoxy, halogen, NO_2, C_1-C_2 haloalkyl, C_1-C_2 alkylthio, C_1-C_2 alkylsulfonyl, C_1-C_2 alkoxycarbonyl, C_1-C_2 dialkylaminosulfamoyl, E_1 is H, Cl, Br, CH_3 or SCH_3, A is ▲ mathematical formula, chemical formula, table There are ▼￥A-1￥, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼￥A-2￥, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼￥A-3￥, ▲There are mathematical formulas, chemical formulas, tables, etc. Yes▼￥A-4￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥A-5￥, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥A-6￥, and X is H, C_1-C_4 Alkyl, C_1-C_4 alkoxy, C_1-C_4 haloalkoxy, C_1-C_
4 haloalkyl, C_1-C_4 haloalkylthio, C
_1-C_4 alkylthio, halogen, C_2-C_5
Alkoxyalkyl, C_2-C_5 alkoxyalkoxy, amino, C_1-C_3 alkylamino or di(C_1-C_3 alkyl)amino, and Y is H, C
_1-C_4 alkyl, C_1-C_4 alkoxy, C
_1-C_4 haloalkoxy, C_1-C_4 haloalkylthio, C_1-C_4 alkylthio, halogen, C
_2-C_5 alkoxyalkyl, C_2-C_5 alkoxyalkoxy, amino, C_1-C_3 alkylamino, di(C_1-C_3 alkyl)amino, C_3-
C_4 alkenyloxy, C_3-C_4 alkynyloxy, C_2-C_5 alkylthioalkyl, C_2-
C_5 alkylsulfinyl alkyl, C_2-C_5
Alkylsulfonylalkyl, C_1-C_4 haloalkyl, C_3-C_5 cycloalkyl, C_2-C_4
Alkynyl, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or N (OCH_
3) CH_3, m is 2 or 3, L_1 and L_2 are independently O or S, and R_
a and R_b are independently C_1-C_2 alkyl; R_c is H or CH_3; Z is CH or N; , chemical formulas, tables, etc. ▼￥J-2￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥J-3￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥J-4￥, ▲ Mathematical formulas, chemical formulas , tables, etc.▼￥J-5￥, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥J-6￥, Y_1 is O or CH_2, X_1 is CH_3, OCH_3, OC_2H_5, or OCF_2H_ , Y_2 is H or CH_3, X_2 is CH_3, OCH_3 or SCH_3, Y_3 is CH_3, CH_2CH_3 or CH_2
CF_3 and X_3 is CH_3 or OCH_3 and X_4 is C
H_3, OCH_3, OC_2H_5, Cl, F, Br
, I, OCF_2H, CH_2F, OCH_2CH_2
F, OCH_2CHF_2, OCH_2CF_3 or CF_3, Y_4 is H, CH_3, OCH_3, OC_2H_5,
CH_2OCH_3, NHCH_3, N(OCH_3)
CH_3, N(CH_3)_2, CH_2CH_3,
CF_3, SCH_3, OCH_2CH=CH_2, O
CH_2C≡CH, CH_2OC_2H_5, OCH_
2CH_2OCH_3, CH_2SCH_3, C(O)
R_c, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, OCF_2H, S
CF_2H or cyclopropyl, provided that 1) When X or X_4 is F, Cl, Br or I, Z is CH, and Y is OCH_3, OC_2H_5, OCF_2H, NH_2
, NHCH_3, N(OCH_3) CH_3 or N(
CH_3)_2, and Y_4 is OCH_3, O
C_2H_5, OCF_2H, NHCH_3, N(OC
H_3) CH_3 or N(CH_3)_2, 2) the total number of carbons in Q must be 8 or less, 3) X,
4) When Y, 5) In compounds of formula Id and Ie, Q is 1H-1,2
,4-triazol-1-yl, Z is C
6) when Y_4 is cyclopropyl, X_4 is other than Cl, F, Br or I, and 7) when W is S, R is H and A is A-1
, J is J-1, and Y and Y_4 are C
H_3, OCH_3, OC_2H_5, CH_2OCH
_3, C_2H_5, CF_3, SCH_3, OCH_
2CH=CH_2, OCH_2C≡CH, OCH_2C
Compounds of H_2OCH_3, CH(OCH_3)_2 or ▲mathematical formula, chemical formula, table, etc.▼] and their agriculturally suitable salts. 2. Q is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-1￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-2￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-3 ¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-4¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-5¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-6¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-7¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-9¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-10¥, ▲Mathematical formulas There are , chemical formulas, tables, etc. ▼￥Q-11￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-12￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-13￥, ▲ Mathematical formulas, chemical formulas , tables, etc.▼￥Q-14￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-15￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-16￥, ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼￥Q-17￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥￥Q-18￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-19￥, ▲There are mathematical formulas, chemical formulas, tables, etc. Yes▼￥Q-20￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-21￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-22￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ¥Q-23¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-24¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-25¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q -26￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-27￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-28￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-29 ¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-30¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-31¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-32¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-33￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥￥Q-34￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-35￥, ▲Mathematical formulas There are , chemical formulas, tables, etc. ▼￥Q-36￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-37￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-38￥, ▲ Mathematical formulas, chemical formulas , tables, etc.▼￥Q-39￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-40￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-41￥, ▲Mathematical formulas, chemical formulas, tables, etc. etc.▼￥Q-43￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥￥Q-44￥, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥￥Q-45￥, and R_1 is H, Cl , CH_3 or OCH_3,
R_2 is H, F, Cl, CH_3, OCH_3 or C
F_3, R_3, R_4, R_5, R_6, R_
7, R_8, R_9 and R_1_0 are independently H or CH_3, n' is 0 or 1, R_3' is H, SH, C_1-C_3 alkyl, C_1
-C_4 alkylthio, C_3-C_4 alkenylthio, C_3-C_4 alkynylthio, C_1-C_3 cyanoalkylthio, SCH_2CO_2CH_3, SCH
_2CO_2C_2H_5, SCH_2(O)CH_3
, halogen, C_1-C_3 alkoxy or OCH_
2CH=CH_2, R_3″ is H, CH_3, Cl or Br, and W′
is O or S, W″ is O, S or NR_1_1, and R_1_1 is H, C_1-C_3 alkyl or CH_
Compounds of formula ¥Ia¥, ¥Ib¥ and ¥Ic¥ according to claim 1, wherein 2CH=CH_2. 3, E is H, A is A-1, X is CH_3, OCH_3, OC_2H_5, Cl or Br, Y is H, CH_3, OCH_3, C_2H_5, OC_
2H_5, CH_2OCH_3, CF_3, OCF_2
H, cyclopropyl, OCH_2CF_3, NHCH_
3. N(CH_3)_2, CH(OCH_3)_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, n' is 0, and R_3' and R_3'' are independently HNCH_3 or Cl, The compound according to claim 2, wherein R is H and W is O. 4. The compound according to claim 3, where n is 0. 5. Y is C_1-C_2 Alkyl, OCH_3 or O
The compound according to claim 4, which is CF_2H. 6, R_1 is H, R_2 is H or Cl,
The compound according to claim 5, wherein Z is CH. 7. Compound of formula ¥Ia¥ according to claim 6. 8. A compound according to claim 6 having the formula \Ib\. 9. A compound according to claim 6 having the formula \Ic\. 10, Q is Q-1, Q-2, Q-3, Q-5, Q-7,
Q-10, Q-11, Q-15, Q-16, Q-20,
Q-23, Q-28, Q-36 or Q-39,
A compound according to claim 7. 11, Q is Q-1, Q-2, Q-3, Q-5, Q-7,
Q-10, Q-11, Q-15, Q-16, Q-20,
Q-23, Q-28, Q-36 or Q-39,
A compound according to claim 8. 12, Q is Q-1, Q-2, Q-3, Q-5, Q-7,
Q-10, Q-11, Q-15, Q-16, Q-20,
Q-23, Q-28, Q-36 or Q-39,
A compound according to claim 9. 13. The compound according to claim 10, in which W'' is S. 14. The compound according to claim 11, in which W'' is S. 15. The compound according to claim 12, wherein W'' is S. 16. R is H, W is O, and Q is ▲a numerical formula, chemical formula, table, etc.▼￥Q-46 ¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-47¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-48¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-49¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-50￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥￥Q-51￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-52￥, ▲Mathematical formulas There are , chemical formulas, tables, etc. ▼￥Q-53￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-54￥, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼￥Q-55￥, ▲ Mathematical formulas, chemical formulas , tables, etc.▼￥Q-56￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-57￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-58￥, ▲Mathematical formulas, chemical formulas, tables, etc. There are ▼￥Q-59￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥￥Q-60￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-61￥, ▲There are mathematical formulas, chemical formulas, tables, etc. Yes▼￥Q-62￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-63￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-64￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ￥Q-65￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-66￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-67￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q -68 yen, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ￥ Q-69 yen, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ￥ Q-70 yen, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ￥ Q-71 ¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-72¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-73¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼¥Q-74¥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-75￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥￥Q-76￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-77￥, ▲Mathematical formulas , chemical formulas, tables, etc.▼¥Q-78¥, ▲Mathematical formulas, chemical formulas, tables, etc.▼¥Q-79¥, ▲Mathematical formulas, chemical formulas, tables, etc.▼¥Q-80¥, ▲Mathematical formulas, chemical formulas , tables, etc.▼￥Q-81￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-82￥, ▲There are mathematical formulas, chemical formulas, tables, etc.▼￥Q-83￥, ▲Mathematical formulas, chemical formulas, tables, etc. etc. are selected from the group consisting of
or CH_3, R_1_1 is H, CH_3, C_2H_5, C_1-C
_3 alkylthio, SCH_2CH=CH_2, SCF
_2H, OCH_2 or OCH_2CH_3, R_1_6 is H or Cl, R_1_7 and R_1_8 are independently H, CH_3
or OCH_3, R_1_9 and R_2_0 are independently CH_3 or OCH_3, W″ is O, S or NR_1_1, and R_1
Compounds of formula \Id\ and \Ie\ according to claim 1, wherein _2 is as defined above. 17, J is J-1, E_1 is H, n' is 0, and Q is Q-46, Q-47, Q-48, Q-49, Q-5
2, Q-53, Q-54, Q-55, Q-56, Q-5
9, Q-61, Q-62, Q-63, Q-66, Q-6
7, Q-69, Q-72, Q-75, Q-78, Q-8
2, Q-83, and phenyl. 18, X_4 is CH_3, OCH_3, OCH_2CH
_3 or Cl, and Y_4 is CH_3, CH_2CH_3, OCH_3, C
The compound according to claim 17, which is H(OCH_3)_2 or CH_2OCH_3. 19. The compound according to claim 18, wherein n is 0. 20, Y_4 is CH_3, CH_2CH_3 or OC
20. The compound of claim 19, which is H_3. 21, a compound according to claim 20 of the formula \Id\. 22, a compound according to claim 20 having the formula \Ie\. 23, Q is Q-46, Q-47, Q-48, Q-49,
Q-52, Q-53, Q-54, Q-55, Q-56,
Q-59, Q-61, Q-62, Q-63, Q-66,
Q-67, Q-69, Q-72, Q-75, Q-78,
22. A compound according to claim 21, which is Q-82, Q-83 and phenyl. 24, Q is Q-46, Q-47, Q-48, Q-49,
Q-52, Q-53, Q-54, Q-55, Q-56,
Q-59, Q-61, Q-62, Q-63, Q-66,
Q-67, Q-69, Q-72, Q-75, Q-78,
23. A compound according to claim 22, which is Q-82, Q-83 and phenyl. 25. The compound according to claim 1, which is N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-(isoxazol-3-yl)-2-thiophenesulfonamide. 26,3-(isoxazol-3-yl)-N-[(4
-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-thiophenesulfonamide,
A compound according to claim 1. 27, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(isoxazole-3-
2-thiophene sulfonamide. 28,3-(5-chloro-1H-1,2,4-triazol-1-yl)-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-thiophenesulfonamide , a compound according to claim 1. 29, N-[(4-methoxy-6-methylpyrimidine-
2-yl)aminocarbonyl-3-(1H-pyrrole-
1-yl)-2-thiophenesulfonamide. 30, N-[(4-methoxy-6-methyl-1,3,5
-triazin-2-yl)aminocarbonyl-3-(1
2. The compound according to claim 1, which is H-pyrrol-1-yl)-2-thiophenesulfonamide. 31, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(1H-pyrrole-1-
2-thiophene sulfonamide. 32, N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-(1H-pyrrol-1-yl)-2-thiophenesulfonamide according to claim 1. Compound. 33, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(1H-1,2,4-triazol-1-yl)-3-pyridine sulfonamide. A compound according to scope 1. 34, N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-3-(1H-pyrrol-1-yl)-2-thiophenesulfonamide, a patent claim A compound according to item 1 in the range. 35, N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-3-(1H-
2. The compound according to claim 1, which is pyrrol-1-yl)-2-thiophene sulfonamide. 36, N-[(4-chloro-6-methoxypyridimine-
2-yl)aminocarbonyl]-3-(1H-pyrrol-1-yl)-2-thiophenesulfonamide,
A compound according to claim 1. 37, N-[(4-methoxy-6-methylpyrimidine-
2-yl)aminocarbonyl]-3-(2-methyl-4
-thiazolyl)-2-thiophenesulfonamide. 38, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-(2-methyl-4-thiazolyl)-2-thiophenesulfonamide according to claim 1. Compound. 39. A composition suitable for controlling undesired plant growth, comprising an effective amount of a compound according to claim 1 and at least one surfactant or solid or liquid diluent. 40. A composition suitable for controlling undesired plant growth, comprising an effective amount of a compound according to claim 2 and at least one surfactant or solid or liquid diluent. 41. A composition suitable for regulating undesired plant growth, comprising an effective amount of a compound according to claim 3 and at least one surfactant or solid or liquid diluent. 42. A composition suitable for regulating undesired plant growth, comprising an effective amount of a compound according to claim 4 and at least one surfactant or solid or liquid diluent. 43. A composition suitable for controlling undesired plant growth, comprising an effective amount of a compound according to claim 16 and at least one surfactant or solid or liquid diluent. 44. A composition suitable for controlling undesired plant growth, comprising an effective amount of a compound according to claim 17 and at least one surfactant or solid or liquid diluent. 45. A composition suitable for controlling undesired plant growth, comprising an effective amount of a compound according to claim 18 and at least one surfactant or solid or liquid diluent. 46. A composition suitable for regulating undesired plant growth, comprising an effective amount of a compound according to claim 19 and at least one surfactant or solid or liquid diluent. 47. A method for regulating undesirable plant growth, comprising applying an effective amount of a compound according to claim 1 to the site to be protected. 48. A method for regulating undesirable plant growth, comprising applying an effective amount of a compound according to claim 2 to the site to be protected. 49. A method for regulating undesirable plant growth, which comprises applying an effective amount of a compound according to claim 3 to the site to be protected. 50. A method for regulating undesirable plant growth, comprising applying an effective amount of a compound according to claim 4 to the site to be protected. 51. A method for regulating undesirable plant growth, which comprises applying an effective amount of a compound according to claim 16 to the site to be protected. 52. A method for regulating undesirable plant growth, comprising applying an effective amount of a compound according to claim 17 to the site to be protected. 53. A method for controlling undesirable plant growth, which comprises applying an effective amount of a compound according to claim 18 to the site to be protected. 54. A method for controlling undesirable plant growth, comprising applying an effective amount of a compound according to claim 19 to the site to be protected.