GB1592043A - Tetrahydro-1,3,5-thiadiazin-4-one derivatives - Google Patents

Abstract

The tetrahydro-1,3,5-thiadiazin-4-one compounds of the general formula <IMAGE> in which R<1>, R<2> and R<3>, which may be identical or different, each denote an alkyl group having from 1 to 8 carbon atoms, an allyl group, a cycloalkyl group having from 3 to 6 carbon atoms, an alkoxyalkyl group with a total of from 3 to 6 carbon atoms, a benzyl group, phenyl group or substituted phenyl group containing one or more substituents from the group comprising alkyl groups having from 1 to 4 carbon atoms, nitro groups, halogen atoms, alkoxy groups having from 1 to 4 carbon atoms and trifluoromethyl groups, and R<2> and R<3> may also represent hydrogen atoms, are useful compounds for the control of insects and mites.

Description

(54) TETRAHYDRO-1 ,3,5-THIADIAZIN-4-ONE DERIVATIVES (71) We, NIHON NOHYAKU CO. LTD., a corporation organised under the laws of Japan of 1--22-5, Nihonbashi, Chuo-ku, Tokyo, Japan, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to tetrahydro - 1,3,5 - thiadiazin - 4 - ones represented by the general formula:

wherein R', R2 and R3, which may be the same or different, each represent an alkyl group of C, to Ca, allyl group, cycloalkyl group of C3 to C6, alkoxyalkyl group having a total of 3 to 6 carbon atoms, benzyl group, phenyl group or substituted phenyl group having one or two substituents selected from alkyl groups of C, to C4, nitro groups, halogen atoms, alkoxy groups of C, to C4, and trifluoromethyl groups, R' may also represent a p-hydroxyphenyl group, R2 may also represent a hydrogen atom or a furfuryl group, and R3 may also represent a hydrogen atom; and acid addition salts thereof. Further, this invention relates also to a process for producing the compounds represented by the above general formula or acid addition salts thereof. Furthermore, this invention relates also to insecticides and miticides containing as active ingredients the compounds represented by the above general formula or the acid addition salts thereof.

The compounds represented by the general formula (l) and the acid addition salts thereof are novel compounds.

The compounds represented by the general formula (I) may be readily synthesized by reacting a carbamoyl chloride represented by the general formula,

wherein R' is the same as defined above, with a thiourea represented by the general formula,

wherein R2 and R3 are the same as defined above, in the presence or absence of a base. This reaction may be represented by the following equation and the compounds represented by the general formula (I) can be obtained in free state:

wherein R', R2 and R3 are as defined above.

On the other hand, a carbamoyl chloride represented by the general formula (Il) and a thiourea represented by the general formula (III) can react without the addition of a base. In this case, the compound represented by the general formula (I) is obtained in the form of a hydrochloride. The reaction is advantageously carried out under the application of heat. Therefore, if it is desirable to obtain the compound represented by the general formula (I) in the form of a hydrochloride, it is convenient to carry out the reaction in this way. When the compound represented by the general formula (I) is desired in a free state, it may be obtained by dissolving the hydrochloride in water and adjusting the pH of the solution to neutral or slightly alkaline. This reaction may be represented by the following equation:

wherein R', R2 and R3 are as defined above.

Thus, the compound represented by the general formula (I) can be synthesized by either of the procedures (A) and (B). It is also possible to convert the compound represented by the general formula (I) into its salt by treating the compound with an acid of the desired type. All of these procedures are included within the scope of this invention.

The carbamoyl chloride used as one of the reactants in this invention can be synthesized, for example, by the following or similar procedures:

J. Org. Chem., 39,2897(1974)

Chem. Abst., 59, 9816f

The above procedures (4) and (5) are an improvement worked out by the present inventors on the procedure (2).

The procedure (I) cannot be applied to the chlorination of aniline derivatives having on their benzene nuclei substituents sensitive to chlorination. In such a case, it is necessary to follow the route of addition reaction in which a dehydrationcondensation product (for example, azomethine or hexahydro-s-triazine) of an aniline derivative and formaldehyde is reacted with phosgene or trichloromethyl chloroformate, as shown in the above procedures (2) to (5). The resulting carbamoyl chloride is not necessarily isolated but the reaction mixture can be used as such in the subsequent reaction with thiourea.

The studies conducted by the present inventors revealed several interesting features of the ring-forming reaction in this invention. When the substituents in the thiourea molecule are different from each other, there is a certain tendency with respect to the position occupied by the substituents R2 and R3 in the ultimate compound of the formula (I). When both R2 and R3 of the thiourea are alkyl groups, the substituent which occupies the position R3 in the compound (I) is generally an alkyl group having a longer carbon chain or a bulky alkyl group having a more branched carbon chain attached to the nitrogen atom, the bulkiness having preference to the chain length of the substituent. Accordingly, if a 1,3-dialkyl thioureahaving straight chain alkyl groups is used, the alkyl group with the larger number of carbon atoms generally occupies the position R3 in the compound of the formula (1). If a thiourea with substituents of approximately the same bulkiness is used, there is sometimes formed a mixture of the compounds having the formulae:

wherein Alk' and Alk2 represent alkyl groups having approximately the same degree of branching. In this respect, a phenylalkyl group exhibits similar tendency to the alkyl group.

In another case where the ring-forming reaction is carried out using a I alkyl - 3 - arylthiourea, the aryl group is introduced in the position R2 of the compound (I). However, even when such a thiourea is used, if the alkyl group is methyl, there is sometimes obtained a mixture of the compound (I) with the methyl group at the position R2 and that with the methyl group at the position R3.

Such a mixture can be separated, in some cases, into both compounds utilizing the difference in solubility.

Some typical examples wherein a mixture is obtained are shown below.

2-Isopropylimino-3-s-butyl-5phenyltetrahydro-1,3,5thiadiazin-4-one NMR(CDCl3) #: 0.90 (t. 3H), 1.15(d. 6H), 1.50(d. 3H), 1.80(m. 2H), 3.48(m. lH), 4.53(m. 1H) 2-s-Butylimino-3-isopropyl-5phenyltetrahydro-1,3,5thiodiazin-4-one NMR(CDCl3) #: 0.87 (t. 3H), 1.1 l(d. 3H), 1.48(d. 6H), 1.80(m. 2H), 3.27(m. lH), 4.77(m. 1H)

2-Phenylimino-3-methyl-5phenyltetrahydro-1,3,5thiadiazin-4-one NMR(CDCl3) #:

2-Methylimino-3,5diphenyltetrahydro I ,3,5-thiadiazine-4-one NMR(CDCl3)#: 3.04(s. 3H: --N-CH3) 4.83(s. 2H: -N-CH-S-)

2-Phenylimino-3-methyl-5isopropyltetrahydro- 1,3,5thiadiazin-4-one NMR(CDCl3)#: 3.35(3H.S: -N-CH3), 4.02(2H.S: -N-CH2-S-) 2-Methylimino-3-phenyl5-isopropyltetrahydro I ,3,5-thiadiazin-4-one NMR(CDCl3) #: 2.95(3H.S: =N-CH3),

It is interesting to note that, as described above, the ring-forming reaction in this invention seems to be associated with the steric structural bulkiness of the R2 and R3 groups.

The starting compounds represented by the formulae (II) and (III) are explained hereafter. R', R2 and R3 are defined as previously described. The alkyl groups having 1 to 8 carbon atoms include straight chain and branched chain alkyl groups and can be shown by, for example, methyl, ethyl, n-propyl, isopropyl, nbutyl, isobutyl, t-butyl, s-butyl, n-pentyl, 3-methylbutyl, n-hexyl, heptyl, n-octyl, 1,1 ,3,3-tetramethylbutyl (t-octyl) and 2-ethylhexyl. The cycloalkyl groups having 3 to 6 carbon atoms include cyclohexyl, cyclopentyl, cyclopropyl and cyclobutyl.

Examples of alkoxyalkyl groups each having a total of 3 to 6 carbon atoms are methoxyethyl, methoxypropyl, ethoxyethyl, propoxyethyl and butoxyethyl.

In the substituted phenyl groups represented by R', R2 and R3, which may be the same or different, the substituent halogens are fluorine, chlorine, bromine and iodine; and the substituent alkyl or alkoxy groups of C, to C4 include straight chain and branched chain groups. Typical examples of such substituted phenyl groups are chlorophenyl, dichlorophenyl, fluorophenyl, methoxyphenyl, ethoxyphenyl, isopropoxyphenyl, trifluoromethylphenyl, chlorotolyl, chloromethoxyphenyl, tolyl and dimethylphenyl groups.

The reaction in this invention is preferably carried out in a solvent which does not seriously interfere with the progress of the reaction. Suitable solvents for use here are: water; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, cyclohexanone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and ethyl ether; halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene; alcohols such as ethanol and propanol; esters of aliphatic acids such as ethyl acetate; aliphatic amides such as dimethylformamide and dimethylacetamide; dimethyl sulfoxide; and other solvents which do not seriously interfere with the reaction. These solvents can also be used in combinations such as mixtures of water and organic solvents and mixtures of organic solvents.

The bases for use in the reaction include inorganic bases such as potassium hydroxide, sodium hydroxide, aqueous ammonia, potassium carbonate, sodium carbonate and sodium hydrogen carbonate; and organic bases such as triethylamine, pyridine, and 1,8 - diazabicyclo - 15,4,0i - 7 - undecene. These bases are used, in most cases, in the form of an aqueous solution, although they can be used in powder form, if available.

The reaction temperature can be selected from a wide range of -10" to 200"C, but the preferable temperature range is from room temperature to about 100"C. for the procedure (A) and from 60 to 1300C. for the procedure (B).

Since the reaction between a thiourea and N - chloromethyl - N - phenylcarbamoyl chloride is equimolar, the reactants are used in an equimolar ratio or in a slight excess of either reactant. The amount to be used of the base for I mole of either reactant is 2 moles or in slight excess for the procedure (A), and I mole or in slight excess for the procedure (B).

After completion of the reaction, the reaction mixture is treated with a suitable solvent to extract the compound represented by the formula (I), and the extract solution is washed, dried and freed from the solvent to obtain the compound (I) in the form of crystals or an oil, which, if necessary, is further purified.

When the compound represented by the formula (I) is desired to be recovered in the form of a salt, either the procedure (B) is followed or the compound (I) is treated with a desired acid. The acids for use in preparing the salt are common inorganic or organic acids including HCI, HBr, H2SO4, H3 PO4, HNO3, HClO4, CH3COOH, CCI3COOH, formic acid and benzenesulfonic acid.

Typical Examples of the compounds represented by the formula (I) are given below. In the case of

Compound Substituent group Physical No. R1 R R3 property CH3 C2H5 C2H5 m.p. 82-84 C 2 CH3 i-C3H7 i-C3H, m.p. 76-77 C 3 CH3 n-C3H7 t-C4H9 m.p. 81-82 C 4 CH3 n-C6H13 n-C6H13 m.p. 63-65 C 5 C2H5 CH3 CH3 m.p. 43-44 C 6 C2H5 CH3 t-C4H9 m.p. 68-69 C 7 C2H5 C2H5 C2H5 m.p. 68-70 C 8 C2H5 i-C3H7 i-C3H7 m.p. 61-62 C 9 CH2CH=CH2 CH3 CH3 nD20 1.5615 10 CH2CH=CH2 CH3 i-C3H7 nD20 1.5380 11 CH2CH=CH2 C2H5 C2H5 nD20 1.5397 12 CH2CH=CH2 n-C3H7 n-C3H7 nD20 1.5285 13 n-C3H7 CH3 i-C3H7 nD20 1.5310 14 n-C3H7 i-C3H7 i-C3H7 nD20 1.5166 15 n-C3H7 Benzyl i-C3H7 nD20 1.5185 16 i-C3H7 CH3 CH3 m.p. 92-93 C 17 i-C3H7 CH3 C2H5 m.p. 93-95 C 18 i-C3H7 CH3 i-C3H7 m.p. 87-88 C 19 C3H7 CH3 Benzyl m.p. 106-108 C 20 i-C3H7 CH3 n-C6H13 nD20 1.5199 21 i-C3H7 CH3 2-Ethylhexyl nD20 1.5180 22 i-C3H7 CH3 n-C8H17 nD20 1.5167 23 i-C3H7 C2H5 C2H5 nD20 1.5264 24 i-C3H7 n-C3H7 n-C3H7 nD20 1.5160 25 n-C4H9 CH3 i-C3H7 m.p. 84-85 C 26 n-C4H9 C2H5 s-C4H9 m.p. 81-82 C 27 i-C4H9 i-C3H7 i-C3H7 m.p. 93-94 C 28 i-C3H7 CH3 Cyclohexyl m.p. 98-99 C 29 s-C4H9 CH3 i-C3H7 m.p. 82-83 C 30 s-C4H9 C2H5 i-C3H7 m.p. 89-90 C Compound Substituent group Physical No. R' R2 R3 property 31 t-C4H9 CH3 CH3 m.p. 51-52 C 31 CH3 n-C3H7 nD20 1.5273 t-C4H9 33 t-C4H9 CH3 i-C3H7 m.p. 62-63 C 34 t-C4H9 CH3 n-C4H9 nD20 1.5185 35 t-C4H9 CH3 s-C4H9 m.p. 83-84 C 36 t-C4H9 CH3 i-C4H9 m.p. 77-78 C 37 t-C4H9 CH3 t-C4H9 m.p. 107-108 C 38 t-C4H9 CH3 Benzyl m.p. 125-127 C 39 t-C4H9 CH3 n-C6H13 nD20 1.5122 40 t-C4H9 CH3 n-C8H17 m.p. 58-59 C 41 t-C4H9 C2H5 C2H5 nD20 1.5235 42 t-C4H9 C2H5 t-C4H9 nD20 1.5189 43 t-C4Hg n-c3H7 n-C3H7 nD20 1.5160 44 t-C4Hg n-C3H7 n-C4Hg nD20 1.5096 45 t-C4Hg n-C4Hg n-C4Hg nD20 1.5065 46 t-C4Hg n-C4Hg t-C4Hg nD20 1.5085 47 t-C4Hg Benzyl t-C4Hg m.p. .p. 75-76 C 48 t-C4Hg i-C3H7 t-C8H17 m.p. .p. 89-91 C 49 t-C4H9 n-C8H17 n-C8H17 nD20 1.5003 50 n-C6H13 CH3 i-C3H7 nD20 1.5195 51 n-C6H13 i-C3H7 i-C3H7 nD20 1.5188 52 Cyclohexyl i-C3H7 i-C3H7 nD20 1.5205 53 Cyclohexyl CH3 t-C4H9 nD20 1.5210 54 Benzyl CH3 CH3 m.p. 93-95 C 55 Benzyl C2H5 C2H5 nD20 1.5630 56 Benzyl i-C3H7 n-C3H7 nD20 1.5653 57 Benzyl Benzyl i-C3H7 nD20 1.5780 58 t-C8H17 CH3 CH3 m.p. 66-68 C 59 t-C8H17 CH3 i-C3H7 nD20 1.5100 60 t-C8H17 CH3 CH2=CHCH2 nD20 1.5210 61 t-C8H17 CH3 n-C4H9 nD20 1.5112 Substituent group No. R R R property 62 t-C8H17 CH3 i-C4H9 nD20 1.5110 63 t-C8H17 CH3 t-C4H9 m.p. 91-93 C 64 n-C8H17 CH3 CH3 nD20 1.5190 65 n-C8H17 CH3 i-C3H7 nD20 1.5185 66 i-C3H7 Phenyl CH3 m.p. 174-176 C

cH5 3 67 i-C3H7 CM3 BY m.p. 91--92"C CH3 68 i-C3H7 t3 CH3 m.p. 139-141"C 69 t-C4H9 Phenyl CH3 m.p. 125-127 C

70 t-C4Hg < CM3 m.p. 165--166"C 71 t-C4M6 CM3 m.p. 150-151"C 72 t-C4H9 CH,CH3 CH3 113-115"C 73 t-C4H9 Phenyl C2H5 m.p. 117-120 C 74 t-C4Hg Phenyl n-C3H7 m.p. 109-110 C 75 t-C4H9 Phenyl i-C3H7 m.p. 136-137 C 76 t-C4Hg Phenyl n-C4Hg m.p. 115-116 C 77 t-C4Hg Phenyl t-C4Hg m.p. 133-134 C 78 t-C4Hg Phenyl Phenyl m.p. 111-112 C 79 t-C4H9 Phenyl n-C8H17 m.p. 59 C

CHg 80 t-C4Hg t > ~ C2H5 m.p. 157-1580C CH3 81 t-C4M9 ~t~ C3H6 m.p.103--104"C Substituent group property No. R R R

CH? 82 t-C4Hg CM3 m.p. - l24-l250C CL 83 t-C4Hg 4 Cl C CM3 m.p. 140-141"C 84 t-C4Hg e CCH3 C2Hs m.p. - 116-l170C 85 Benzyl Phenyl CH3 m.p. 109-110 C 86 Benzyl Phenyl Cyclohexyl m.p. 101-102 C

CHOW 87 Benzyl < 53 i-C3M7 m.p. l3l-l320C a 88 t-C8H,7 Phenyl CH3 m.p. 121-122 C

CHO 89 t-C8H,7 CH5O n-C3H7 m.p.118-119"C 3F3 90 t-C,H,,- s-C,H, m.p. 93--940C 91 i-C3H7 CH3 Phenyl NMR spectrum (described before) 92 i-C3H7 CH3 H nD20 1.5095 93 t-C4H9 CH2=CHCH2 CH2=CHCH2 m.p. 62-63 C 94 t-C4Hg n-C3H7 Benzyl m.p. 45-46 C 95 t-C4Hg (CH3)2CHCH2CH2 nD20 1.5477 t-C4H9 96 t-C4H9 Cyclohexyl Cyclohexyl nD20 1.5610 97 n-C6H13 CH3 CH3 nD20 1.5245 Compound Substituent group Physical No. R' R2 R3 property 98 n-C6H17 n-C4H9 i-C3H7 nD20 1.5265 99 Cyclohexyl i-C4H9 t-C4H9 nD20 1.5565 100 Cyclohexyl n-C6H13 i-C3H7 nD20 1.5781 101 t-C8H17 C2H5 C2H5 nD20 1.5116

C2M6 102 n-C4H9-CMCH2 CH3 i-C3H7 nD 1.51.02 C3M6 103 n-C4H8-CHCM2 CH2=CHCH2 i-C3H7 nD 1.5178 104 s-C4Hg Cyclopentyl t-C4Hg m.p. 130-130.5 C 105 s-C4H9 C2H5OCH2CH2 i-C3H7 nD26 1.5019

106 s-C4H9 cL CL m.p. 130--131"C 107 t-C4Hg H s-C4Hg m.p. 98-100 C 108 t-C4H9 C2H5 H m.p. 221-222 C 109 t-C4Hg H H m.p. 123-125 C 110 Cyclopentyl CH3 CH3 nD24 1.5370 111 Cyclopentyl i-C3H7 i-C3H7 nD24 I 1.5156 112 CH3OCH2CH2CH2 CH3 i-C3H7 nD24 1.5043 113 CH3OCH2CH2CH2 CH3 Benzyl nD24 1.5590 114 Cyclopentyl Benzyl Benzyl m.p. 85-86 C In the case of

Compound No. R2 R3 Physical property 115 CH3 CH3 m.p. 68-70 C 116 CH3 C2H5 nD20 1.6034 117 CH3 n-C3H7 nD20 1.5902 118 CH3 i-C3H7 m.p. 72-73.5 C 119 CH3 n-C4Hg m.p. 30-35 C 120 CH3 t-C4H9 m.p. 87-90 C 121 CH3 Benzyl m.p. 90-92 C 122 CH3 n-C8H17 nD20 1.5551 123 CH3 H m.p. 101-103 C

124 CH3 CH5 m.p. 113-l140C 125 C2H5 C2H5 m.p. 55-58 C 126 C2H5 n-C3H7 nD20 1.5800 127 C2H5 i-C3H7 m.p. 69-71 C 128 C2H5 n-C4H9 nD20 1.5709 129 C2H5 i-C4H9 m.p. 85-88 C 130 C2H5 s-C4H9 m.p. 88-89 C 131 C2H5 t-C4H9 m.p. 93-94 C 132 C2H5 Cyclohexyl m.p. 133-135 C 133 C2H5 n-C8H17 nD20 1.5468 134 n-C3H7 n-C3H7 nD20 1.5090 135 n-C3H7 i-C3H7 nD20 1.5646 136 n-C3H7 s-C4H9 nD20 1.5579 137 n-C3H7 t-C4Hg m.p. 65-67 C 138 n-C3H, Cyclohexyl nD20 1.5697 Compound No R R Physical property 139 CH2=CHCH2 CH2=CHCH2 nD20 1.5941 140 CH2=CHCH2 n-C3H7 nD26 1.5753 141 CH2=CHCH2 i-C3H7 nD26 1.5722 142 CH2=CHCH2 s-C4H9 nD26 1.5719 143 CH2=CHCH2 t-C4H9 m.p. 46-47 C 144 i-C3H7 i-C3H7 m.p. 92-94 C 145 i-C3H7 t-C4Hg m.p. 104-106 C 146 n-C4Hg n-C4Hg nD20 1.5604 147 n-C4Hg i-C3H7 nD20 1.5580 148 i-C4H9 i-C4H9 m.p. 82-83 C 149 i-C4H9 i-C3H7 m.p. 80-82 C 150 i-C4Hg t-C4Hg m.p. 75-77 C 151 s-C4Hg s-C4Hg nD20 1.5561 152 s-C4Hg t-C4Hg nD20 1.5544 153 n-C6H13 i-C3H7 nD26 1.5464 154 n-C6Hl3 n-C6Ha3 nD20 1.5420 155 Cyclohexyl t-C4Hg m.p. 86-89 C 156 i-C3H7 t-C8H,7 nD25 1.5382 157 s-C4H9 t-C8H17 nD20 1.5461 158 Benzyl i-C3H7 m.p. 124-125 C 159 Benzyl t-C4Hg nD26 1.5910 160 n-C8H17 i-C3H7 nD20 1.5400 161 n-C8H,7 s-C4Hg nD20 1.5351 162 Phenyl C2H5 m.p. 113-115 C 163 Phenyl s-C4Hg m.p. 134-135.5 C

164 a e i-C3M7 m.p. 175-1770C 165 CH3Ot- C2H6 m.p. 116-1170C Compound R R Physical No. property

CH3 CH3 CL C, m.p. 121-123"C 166 CL 167 F i-C3M7 m.p. 182-184"C CFs 168 s-C4H9 OD3O 1.5538 169 Phenyl Phenyl m.p. 193--194"C OCH3 170 ~9~ C2M5 m.p.136--137"C Ct CL 171 CH3 4 C3 m.p. 111--1120C Ct 172 CE t n-C3H7 m.p.146--1470C 173 s-C4Hg i-C3H7 NMR spectrum 174 i-C3H7 s-C4Hg NMR spectrum described 175 CH3 Phenyl NMR spectrum before 176 Phenyl CH3 NMRspectrum CH3 177 CH3 / < Obtained as a CL- mixture with compound No.166 178 H H m.p. 176"C (decomp.) 179 CH3OCH2CH2 i-C3H7 nD 1.5640 180 CH3OCH2CH2 t-C4Hg nD 1.5559 Compound R2 R3 Physical No. property 181 C2H5OCH2CH2 i-C3H7 nD20 1.5572 182 C2H5OCH2CH2 t-C4H9 m.p. 74-75.5 C 183 Cyclopentyl t-C4Hg m.p. 103-104 C 184 t-C4Hg t-C4Hg m.p. 109-115 C

185 ~ < > CL < -CL m.p. 172-l750C In the case of

Compound X R2 R3 Physical No. property 186 4-Cl H i-C3H7 m.p. 190-197 C (decomp.) 187 4-Cl H t-C4H9 m.p. 210-214 C (decomp.) 188 4-Cl CH3 CH3 m.p. 98-100 C 189 4-Cl CH3 i-C3H7 m.p. 106-108 C 190 4-Cl C2H5 C2H5 m.p. 123-125 C 191 4-Cl C2H5 t-C4H9 m.p. 154-157 C 192 4-Cl n-C3H7 n-C3H7 m.p. 81-82 C 193 4-Cl n-C3H7 i-C3H7 m.p. 61-63 C 194 4-Cl i-C3H7 i-C3H7 m.p. 127-129 C 195 4-Cl n-C3H7 t-C4H9 m.p. 68-69 C 196 4-cl i-C3H7 t-C4H9 m.p. 123-125 C 197 4-Cl s-C4H9 s-C4H9 m.p. 102-103 C 198 4-Cl s-C4H9 t-C4H9 m.p. 99-100 C 199 4-Cl CH2=CHCH2 CH2=CHCH2 nD30 1.6003 200 4-Cl CH2=CHCH2 i-C3H7 nD30 1.5833

Compound X R2 R3 Physical No. property

202 4-C1 CH2=CHCH2 ~ ,nD9 1.6221 203 4-Cl CH2 \=/ i-C3H7 nD8 1.5978 204 4-C1 CH2 < t-C4Hg m.p. 87-890C 205 4-Cl F i-C3H7 m.p. l53-1550C 206 4-C1 i-C3H., t-C8M17 m.p. 124--125"C 207 4-C1 CH3OC2H4 i-C3H7 nD 1.5728 208 4-Cl 4 t-C4Hg m.p. 147--148"C 209 4-C1 < CH3 m.p. 187--188"C Ctl3 210 4-Ci eCH3 CH3 m.p. 148-1490C 211 4-Cl OCt15 4-C1OCH3 C3H5 m.p. 149-150"C 212 4-Cl CH3 n-C6H13 m.p. 75-76 C 213 3-Cl CH3 CH3 m.p. 111-112 C (HCl salt: m.p.

180-183 C decomp.) 214 3-Cl CH3 i-C3H7 m.p. 108-111 C 215 3-Cl C2H5 C2H5 m.p. 106-108 C (HCl salt: m.p.

199-200 C) 216 3-Cl C2H5 t-C4H9 m.p. 62-63 C 217 3-Cl CH2CH=CH2 i-C3H7 nD19 1.5857 (HCl salt: m.p.

179 C decomp.) Compound X R R Physical No. property

218 3-C1 C H2C H =C H2 t-C4Hg n'91.5796 219 3-C1 CH2CH=CH 9 C H2 < 1.6107 220 3-C1 i-C3H, i-C3H7 m.p. 81-82"C 221 3-C1 i-C3H7 t-C4Hg m.p. 113 - 115 C (MCI salt: m.p.

152"C decomp.) 222 3-C1 i-C3H7 t-C8H17 nod91.5406 223 3-C1 i-C4Hg t-C4Hg nO 1.5542 224 3-C1 s-C4Hg s-C4Hg n,:" 1.5652 225 3-C1 s-C4Hg t-C4Hg m.p. 75-76"C (MCI salt: m.p.

1860C decomp.) 226 3-C1-CH3 C H3 m.p. 185-186"C Wj3 227 3-Cl CM3 m.p. 148-149"C 228 3-C1 CM3OC4H9 i-C3H7 nO 1.5731 229 3-Cl C H3O C2H4 t-C4Hg nO 1.5711 230 3-C1 i-C3H7 e m.p. - 105-l060C 231 3-Cl m.p. l58-1590C 232 3-C1 n-C3H7 t-C4Hg nD221.5740 233 3-C1 q i-C3H7 nO 1.5750 234 3-C1 n-C3H13 i-C3H7 nO 1.5635 C H3 235 3-CI -CM2CM3CMCH3 s-C4Hg nO 1.5518 236 3-C1 n-C4Hg t-C4Hg nod31.5600 Compound X R R Physical No. property

CH3 237 3-C1 -C i-C3H7 m.p. 158-1590C 238 2-Cl CH3 CH3 m.p. 142-144 C (HCl salt: m.p.

198-200 C decomp.) 239 2-Cl C2H5 C2H5 m.p. 90-92 C (HCl salt: m.p.

167-170 C decomp.) 240 2-Cl CH3 i-C3H7 nD22 1.5725 241 2-Cl C2H5 t-C4H9 m.p. 94-96 C 242 2-Cl CH2=CHCH2 i-C3H7 nD13 1.5831 243 2-Cl CH2=CHCH2 t-C4H9 m.p. 105-107 C 244 2-Cl i-C3H7 i-C3H7 m.p. 95-96 C 245 2-Cl i-C3H7 t-C4H9 m.p. 88-89 C (HCl salt: m.p.

201 C decomp.) 246 2-Cl i-C3H7 n-C6H13 nD13 1.5581 247 2-Cl i-C3H7 t-C8H17 nD13 1.5822 248 2-Cl s-C4H9 s-C4H9 m.p. 89-90 C 249 2-Cl s-C4H9 t-C4H9 m.p. 67-68 C

250 2-C1 CH2 i-C3H7 m.p. 95-970C 251 2-C1 CH2t CH243 (HCI salt: m.p.

- - 127-1300C decomp.) 252 2-C1 i-C3H7 > m.p. 123--125"C 253 2-C1 i-C4Hg s-C4Hg nD' 1.5582 254 2-C1 n-C6H,3 i-C3H7 n'3 1.5581 255 2-C1 -CH2- i-C3H7 m.p. 75--77"C 256 2-C1 4 C3M5 m.p. 77-790C Compound X R' R3 Physical No. property

257 2-CI Ct CH3 m.p. 167--168"C 258 2-Cl CH3OCH2CH2CH2 t-C4H9 m.p. 87-88 C 259 3-CF3 CH3 i-C3H7 nD30 1.5264 260 3-CF3 C2H5 C2H5 nD30 1.5268 261 3-CF3 C2H5 t-C4H9 nD30 1.5165 262 3-CF3 CH2=CHCH2 i-C3H7 nD24 1.5357 263 3-CF3 n-C3H7 n-C3H7 nD30 1.5233 264 3-CF3 n-C3H7 i-C3H7 nD24 1.5262 265 3-CF3 i-C3H7 i-C3H7 m.p. 67-68 C 266 3-CF3 i-C3H7 t-C8H17 nD24 1.5089 267 3-CF3 CH2=CHCH2 s-C4H9 nD24 1.5392 268 3-CF3 CH2=CHCH2 t-C4Hg nD24 1.5262 269 3-CF3 i-C3H7 s-C4Hg nD24 1.5219 270 3-CF3 i-C3H7 t-C4H9 m.p. 52-53 C (HCl salt: m.p.

160-164 C) 271 3-CF3 i-C4Hg s-C4Hg nD24 1.5140 272 3-CF3 s-C4H9 s-C4H9 nD24 1.5238 273 3-CF3 i-C4H9 t-C4H9 nD24 1.5130 274 3-CF3 s-C4Hg t-C4Hs (HCI salt: m.p.

186.40C decomp.) 275 4-F H i-C3H7 m.p. 188-190 C 276 4-F H t-C4H9 m.p. 205-212 C decomp.

277 4-F CH3 CH3 m.p. 105-106 C (HCl salt: m.p.

221 C decomp.) 278 4-F C2H5 C2H5 m.p. 99-100 C (HCl salt: m.p.

185 C decomp.) 279 4-F CH3 i-C3H7 m.p. 119-120 C (HCl salt: m.p.

202 C decomp.) 280 4-F C2H5 t-C4H9 m.p. 99-100 C 281 4-F n-C3H7 n-C6H13 nD20 1.5596 Compound X R2 R3 Physical No. property 282 4-F i-C3H7 t-C4Hg m.p. 109-110 C 283 4-F s-C4Hg s-C4Hg m.p. 55-56 C 284 4-F s-C4Hg t-C4Hg m.p. 61-62 C 285 4-F i-C3H7 i-C3H7 m.p. 119-120 C

CH3 286 4-F i-C3H7 m.p. 141-142"C 287 4-F C3H5 H m.p. 88-910C 288 4-F q t-C4Hg m.p. 103--104"C 289 4-F CH3 CX2CH=CH2 m.p. 81-82"C a 290 4-F 4 C2M5 m.p. 162-163"C 291 4-Br CH3 CH3 m.p. 136-137 C 292 4-Br C2H5 t-C4H9 m.p. 131-132 C 293 4-Br i-C3H7 i-C3H7 m.p. 121-122 C 294 4-Br i-C3H7 t-C4Hg m.p. 117-118 C 295 4-Br s-C4Hg t-C4Hg m.p. 68-69 C 296 2-CH3 CH3 CH3 m.p. 116-117 C 297 2-CH3 CH3 i-C3H7 nD20 1.5703 298 2-CH3 C2H5 C2H5 m.p. 75-76 C 299 2-CH3 C2H5 t-C4Hg m.p. 920C 300 2-CH3 CH2=CHCH2 t-C4Hg m.p. 90.8 C 301 2-CH3 i-C3H7 i-C3H7 nD20 1.5587 302 2-CH3 i-C3H7 t-C4Hg m.p. 97.5-99 C 303 2-CH3 s-C4Hg t-C4Hg nD20 1.5483 304 2-CH3 n-C6H13 i-C3H7 nD20 1.5421

305 2-CH3 i-C3H7 > m.p. 87"C Compound X R2 R3 Physical No. property

306 2-CM3 CH n i-C,H, m.p. 91. I"C 307 2-CM3 t e nD 1.5568 308 2-CH3 n30 1.5568 CH2 < ) nD20 1.5568 309 4-CH3 CH3 CH3 m.p. 80-81 C 310 4-CH3 CH3 i-C3H7 m.p. 90-91 C 311 4-CH3 CH3 t-C4H9 m.p. 102-105 C 312 4-CH3 C2H5 t-C4H9 m.p. 83-85 C 313 4-CH3 n-C3H7 n-C3H7 m.p. 62-64 C 314 4-CH3 n-c3H7 i-C3H7 m.p. 89-90 C 315 4- Compound X R R Physical No. property 328 3-CH3 s-C4H9 t-C4H9 nD20 1.5546

329 3-CH3 CH2O i-C3H7 m.p. 82-84"C 330 3-CH3 n-C8H13 i-C3H7 nD20 1.5465 331 4-C2H5 CH3 CH3 nD20 1.5922 332 4-C2H5 i-C3H7 i-C3H7 m.p. 81-825 C 333 4-C2H5 i-C3H7 t-C4H9 m.p. 70-72 C 334 4-C2H5 s-C4H9 t-C4H9 m.p. 67.5 C 335 2-C2H5 CH3 CH3 m.p. 122.0 C 336 2-C2H5 CH2=CHCH2 i-C3H7 nD20 1.5601 337 2-C2H5 i-C3H7 i-C3H7 nD20 1.5510 338 2-C2H5 i-C3H7 t-C4H9 nD20 1.5463 339 2-C2H5 s-C4H9 t-C4H9 nD20 1.5401 340 2-C3H7-i CH3 CH3 m.p. 101-102 C 341 2-C3H7-i C2H5 t-C4H9 m.p. 84-85 C 342 2-C3H7-i i-C3H7 i-C3H7 m.p. 85-86 C 343 2-C3H7-i i-C3H7 t-C4Hg m.p. 108-109 C 344 2-C3H7-i s-C4Hg t-C4Hg m.p. 74-76 C 345 2-C3H7-i CH2=CHCH2 CH2=CHCH2 m.p. 93-95 C 346 2-C3H7-i CH2=CHCH2 i-C3H7 nD20 1.5526 347 4-CH3O CH3 i-C3H7 m.p. 69.5 C 348 4-CH3O C2H5 C2H5 m.p. 100 C 349 4-CH3O C2H5 t-C4H9 nD20 1.5591 350 4-CH3O CH2=CHCH2 i-C3H7 m.p. 80.1 C 351 4-CH3O n-C3H7 i-C3H7 m.p. 96-97 C 352 4-CH3O i-C3H7 i-C3H7 m.p. 67-68 C 353 4-CH3O i-C3H7 t-C4H9 m.p. 99-101.5 C

354 4-CM3O n-C3H7 > m.p.85.5 C 355 4-CH3O s-C4H9 t-C4H9 m.p. 63 C Compound X R2 R3 Physical No. property

356 4-CM3O -CH2 < i-C3M7 m.p. 1 140C 357 4-CM3O n-C8H,7 s-C4Hg nO 1.5296 358 4-CM3O < > t-C4Hg m.p. 167-l680C a 359 4-CM3O ~b-CL i-C3M7 m.p. 159.1 C 360 2-CH3O i-C3H7 t-C4H9 m.p. 88.7 C 361 4-F s-C4Hg i-C3H7 NMR spectrum given herein after 362 4-F i-C3H7 s-C4Hg NMRspectrum given herein after In the case of

Compound Physical No. Y Z R2 R3 property 363 H 4-NO2 i-C3H7 H m.p. 160-163 C 364 H 4-NO2 i-C3H7 t-C4Hg m.p. 130-131 C 365 H 4-OH i-C3H7 t-C4Hg m.p. 197-198 C 366 2-NO2 4-NO2 i-C3H7 i-C3H7 m.p. 130-133 C 367 H 4-C2H5O i-C3H7 t-C4H9 m.p. 79-80 C 368 H 4-C2HsO s-C4Hg t-C4Hg m.p. 66-67 C 369 H 4-C2H5O n-C6H13 i-C3H7 m.p. 78-79 C 370 H 4-i-C3H7O CH3 i-C3H7 m.p. 112-113 C 371 H 4-i-C3H7O C2H5 C2H5 nD20 1.5649 372 H 4-i-C3H7O i-C3H7 i-C3H7 m.p. 60-61 C 373 H 4-i-C3H7O i-C3H7 t-C4H9 m.p. 88-89 C 374 H 4-i-C3H7O s-C4H9 t-C4H9 nD20 1.5402 Compound Physical No. Y Z R2 R3 property

375 H 4-i-C3M7O CHge '--CH9- m.p.141--142"C 376 2-CH3 4-CH3 &commat;H, CH3 CH3 nO 1.5900 377 2-CH3 4-CH3 CH3 i-C3H7 nO 1.5674 378 2-CH3 -4-CH3 i-C3H7 i-C3H7 nO 1.5589 379 3 7 4-CH, i-C,H, t-C4Hg m.p. 99-l000C 2-CM3 4-CM3 i-C H 380 2-CH3 4-CH3 s-C4Hg t-C4Hg nO 1.5478 381 2-CH3 3-CH3 CH3 CH3 m.p. 78-79"C 382 2-CH3 3-CH3 C3M5 4 m.p. 151--152"C 383 2-CH3 3-CH3 i-C3H7 i-C3H7 m.p 71-720C 384 2-CH3 3-CH3 i-C3H7 t-C4Hg m.p. 91-92"C 385 2-CH3 3-CH3 s-C4Hg t-C4Hs nO 1.5465 386 2-CH3 3-CH3 CHP t-C4Hg n20 1.5769 387 2-CH3 4-Cl i-C3H7 t-C4H9 m.p. 122-123 C 388 2-CH3 6-CH3 i-C3H7 t-C4Hg m.p. 103-104 C 389 2-CH3 6-CH3 CH3 CH3 nD20 1.5967 390 2-CH3 6-CH3 C2H5 C2H5 m.p. 77-78 C 391 2-C2H5 6-C2H5 CH3 CH3 m.p. 88-89 C 392 2-C2H5 6-C2H5 C2H5 C2H5 nD20 1.5644 393 2-C2H5 6-C2H5 CH3 i-C3H7 m.p. 106-107 C 394 2-C2H5 6-C2H5 CH=CHCH2 CH2=CHCH2 nD20 1.5583 395 2-C2H5 6-C2H5 i-C3H7 i-C3H7 m.p. 89-90 C 396 2-Cl 4-Cl CH3 i-C3H7 m.p. 109-111 C 396 2-Cl 4-Cl C2H5 t-C4H9 m.p. 110-112 C 398 2-Cl 4-Cl i-C3H7 i-C3H7 m.p. 121-123 C 399 2-Cl 4-Cl i-C3H7 t-C4H9 m.p. 130-132 C 400 2-Cl $-Cl s-C4H9 s-C4H9 nD25 1.5634 401 2-Cl $-Cl s-C4H9 t-C4H9 nD20 1.5602 Compound Physical No. Y Z R2 R3 property 402 2-Cl 3-Cl i-C3H7 i-C3H7 m.p. 93-94 C 403 3-Cl 5-Cl CH3 CH3 m.p. 145-147 C 404 3-Cl 3-Cl 5-Cl C2H5 C2H5 m.p. 100-102 C 405 3-Cl 5-Cl n-C3H7 i-C3H7 m.p. 80-82 C 406 3-Cl 5-Cl i-C3H7 i-C3H7 m.p. 81-83 C 407 3-Cl 5-Cl i-C3H7 t-C4H9 m.p. 113-115 C

408 3-C1 5-C1 CH3- i-C3H7 m.p. 90--92"C 409 3-C1 5-Cl i-C3H7 t-C8H.7 m.p. 78-810C 410 3-Cl 5-Cl n-C6H13 i-C3H7 nD23 1.5699 411 3-C1 5-Cl s-C4Hg s-C4Hg nD9 1.5822 412 3-Cl 5-Cl CH2=CHCH2 i-C3H7 nD19.5 1.5962 413 3-Cl 4-Cl C2H5 C2H5 m.p. 86-88 C 414 3-Cl 4-Cl n-C3H7 n-C3H7 nD20 1.5848 415 3-Cl 4-Cl i-C3H7 i-C3H7 m.p. 104-107 C 416 3-Cl 4-Cl i-C3H7 t-C4H9 m.p. 114.5-117.5 C 417 3-C1 4-Cl n-C3H7 s-C4Hg n91.5772 418 3-Cl 4-Cl C2H5 t-C4H9 m.p. 105-107 C 419 3-Cl 4-Cl C2H5 i-C4H9 nD19 1.5912 420 3-Cl 4-Cl n-C3H7 i-C4H9 nD19 1.5769 421 3-Cl 4-Cl CH2=CHCH2 i-C3H7 nD19 1.5920

422 3-C1 4-C1 -CH i-C3H7 nD9 1.6156 423 3-Cl 4-C1 -CHCH2- m.p.118--120"C 424 3-C1 4-C1 CH3 i-C3H7 m.p. 145--147"C 425 3-C1 4-C1 i-C3M7 m.p.127--128"C 426 2-Cl 5-Cl C2H5 t-C4H9 m.p. 91-92 C 427 2-Cl 5-Cl i-C3H7 t-C4H9 m.p. 145-146 C 428 2-Cl 5-Cl s-C4H9 t-C4H9 m.p. 111-112 C Compound Physical No. Y Z R2 R3 property

429 2-C1 5-C1 -CH -CH m.p. 1l9-l200C 430 2-C1 3-C1 C2H5 t-C4Hg m.p. 144--145"C 431 3-CH3 4-CH3 i-C3H7 i-C3H7 m.p. 66--67"C 432 3-CH3 4-CH3 i-C3H7 t-C4Hg m.p. 109--110"C 433 3-CH3 4-CH3 s-C4Hg t-C4Hg m.p. 92--93"C The compounds represented by the formula (I) exhibit strong physiological activity against insects, particularly larvae. The larva which has been treated with the compound or which has ingested a diet treated with the compound dies from abnormal moulting. The insects sensitive to the compound (I) are those of, for example, Hemiptera, Coleoptera, Diptera, Lepidoptera and Orthoptera. Further, many of the compounds (I) have activity to mites; some of them retain miticidal activity to citrus red mite (Panonychus citri McGregor) and two-spotted spider mite (Tetranychus urticae Koch) even at a concentration of 1,000 ppm, the mortality being 80% or more. Accordingly, the compound of this invention is useful as a physiologically active substance to control the pests by applying to plants, grains and others to protect them from injuries inflicted by the above-noted insects and mites.

For instance, the compound of this invention is useful as an active substance to protect rice, corn and other cereals, vegetables, flowers and ornamental plants, tree, cotton, fruit trees, timbers, harvested grains, grasses, lawns and wood products from the attack of pests. The compound is also useful in controlling the insect pests undesirable for life-environment such as mosquitos and flies. It is particularly useful in controlling paddy field pests such as, for example, brown planthopper (Nilaparvata lugens Sty1), smaller brown planthopper (Laodelphax striatellus Fall'en), white-backed planthopper (Sogatellafurcifera Horváth), green rice leafhopper (Nephotettix cincticeps Uhler) and other plant- and leafhoppers.

Further, as compared with conventional insecticides such as phosphorus compounds and carbamate compounds, the compound of this invention is far lower in mammalian acute toxicity and, hence, is far safer. For example, 2 - t butylimino - 3 - isopropyl - 5 - phenyltetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 145) and 2 - t - butylimino - 3 - isopropyl - 5 - p - tolyltetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 318) have LD50 (mice, male) of 10,000 mg/kg or higher. Many other compounds of this invention have LDso (mice, male) of 5,000 mg/kg or higher. As compared with conventional phosphorus insecticides and carbamate insecticides, the compound of this invention exhibits insecticidal activity at lower concentrations, although the activity value varies with the particular target insect. For instance, when the mortality in 7 days after spraying the compound on Sth-instar larvae of brown planthopper is compared, l-naphthyl N-methylcarbamate (commercial insecticide NAC) showed a mortality of only 30% at 200 ppm concentration, whereas the compound of this invention, for example compound No. 145 or No. 318, showed a mortality of 100% at 100 ppm concentration.

This invention provides also a technique for eradicating or controlling injurious insects and mites on the basis of the physiological activity of the compound of this invention. In one of the embodiments of the invention, the compound is directly applied as such to the objects to be protected or to the pests to be controlled (undiluted spray). For instance, the compound of this invention in the form of liquid of 95% or higher purity can be sprayed from an aeroplane, forming a fog of extremely fine liquid particles. The compound of this invention can also be used in treating ponds and pools inhabited by larvae or treating environmental water or irrigation water in which a host is present to render the environment or the feed (host) toxic to larvae.

However, as is customary in the art, the compound of this invention is applied, in most cases, in the form suitable for use by supporting on or diluted with an inert carrier and, if necessary, admixing with auxiliary agents to eradicate or control injurious insects and mites by the physiological activity of the compound.

General suggestions regarding the formulation of insecticidal compositions based on the compound of this invention are described below.

The compound of this invention is blended with a suitable proportion of a suitable inert carrier and, if necessary, auxiliary agents to allow the compound to dissolve, disperse, suspend, mix, impregnate, adsorb or adhere and formed into a suitable preparation such as, for example, solution, suspension, emulsifiable concentrate, oil spray, wettable powder, dust, granule, tablet, pellet, paste or aerosol.

The inert carrier may be solid, liquid or gas. The materials for the solid carrier include plant powders such as, for example, soybean flour, grain flour, wood flour, bark flour, sawdust, tobacco stalk flour, walnut shell flour, wheat bran, powdered cellulose, and extraction residue of plants; fibrous materials such as paper, corrugated fiberboard, and waste cloth; synthetic polymers such as powdered synthetic resins and polymer granules (for example, urea-formaldehyde polymer); inorganic or mineral substances in the form of powder or granule of a suitable particle size such as clays (for example, kaolin, bentonite and acid clay), talcs (for example, talc and pyrophillite), silicic materials (for example, diatomaceous earth, silica sand, mica, synthetic silicates, finely dispersed synthetic silicic acid, etc.), powdered sulfur, activated carbon, pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate and calcium phosphate; chemical fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride; compost, sodium sulfate, sugars and other soluble substances.

These solid carriers are used each alone or in mixtures of two or more. Materials for the liquid carrier are selected from not only solvents for the active compound but also nonsolvents which can disperse the active compound in the presence of a suitable auxiliary agent. Such liquid materials are used each alone or in mixtures of two or more. Examples are water, alcohols (for example, methanol, ethanol, butanol and ethylene glycol), ketones (for example, acetone, methyl ethyl ketone, diisobutyl ketone and cyclohexanone), ethers (for example, ethyl ether, dioxane.

Cellosolves, dipropyl ether and tetrahydrofuran), aliphatic hydrocarbons (for example, gasoline and mineral oils), aromatic hydrocarbons (for example, benzene, xylene, solvent naphtha, and alkylnaphthalenes). halogenated hydrocarbons (for example, dichloroethane, chlorobenzenes and carbon tetrachloride) esters (for example, ethyl acetate, dibutyl phthalate and dioctyl phthalate), acid amides (for example, dimethylformamide, diethylformamide, and dimethylacetamide), nitriles (for example, acetonitrile) and dimethyl sulfoxide. Gaseous carriers include Freons and other aerosol propellants which are gaseous under ordinary conditions.

The auxiliary agents include the following materials which are used in accordance with the purpose of use. Combinations of two or more auxiliary agents are frequently used in some cases no auxiliary agent is used. Surface active agents are used to emulsify, disperse, solubilize oriand wet the active compound.

Examples are polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate. alkylarylsulfonates, naphthalenesulfonic acid condensation products. ligninsulfonate, and higher alcohol sulfate esters. The following substances are used as dispersion stabilizers, spreaders and binders for the active compound: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, dry-distilled wood turpentine, rice bran oil, bentonite and ligninsulfonates.

For the purpose of improving the flow property of solid preparations, use may be made of waxes, stearates and alkyl phosphates. Naphthalenesulfonates and polyphosphates are used as peptizing agents for dispersions. Defoamers such as silicone oil may also be included in the formulation.

The proportion of the active compound in the insecticidal formulation may be varied as required. Suitable proportion of the active compound is generally 0.5 to 20% by weight in dust or granule preparations and 0.1 to 90% by weight in emulsifiable concentrates and wettable powders.

For the purpose of eradicating various insect pest or protecting plants from the attack of various pests, the insecticidal preparation of this invention is used as such, or after being suitably diluted with or suspended in water or other media, and an effective quantity of the preparation is applied to the plants or environment thereof or to the area inhabited by insect pests. For instance, in order to control the insect pests inhabiting a paddy field, the insecticidal preparation of this invention is applied to leaves and stems of rice plants, or to the paddy soil or water of the submerged paddy field.

Application rate of the insecticidal preparation of this invention varies depending on various factors such as, for example, the type of target insect, condition and trend of emergence of pests, weather, environmental conditions, form of the insecticidal preparation, mode of application, site of application, and time of the year. In the case of emulsifiable concentrate and wettable powder, which are applied generally in liquid form, a general practice is to dilute to a final concentration of 0.001% by weight or higher in terms of active ingredient to prepare a spray preparation. Dust and granule are generally applied at a rate of I to 10 kg per 10 ares. However, the above-noted application rates do not limit the scope of this invention.

The insecticidal preparation of this invention can be applied, if necessary, in admixture with or jointly with other pesticides, fertilizers, plant nutrients, and plant growth regulators. Examples of insecticides usable in admixture with the insecticide of this invention are: 0,0udimethyl 0-(4-nitro-3-methylphenyl) thiophosphate (Phenitrothion) 0,0-dimethyl 0-(3-methyl-4-methylthiophenyl) thiophosphate (acid) 0,0-dimethyl S-(carbethoxyphenylmethyl) dithiophosphate (Elsan) 0,0-diethyl 0-(2-isopropyl-4-methylpyrimidyl-6) thiophosphate (Diazinon) 0,0-dimethyl 2,2,2-trichloro- 1 -hydroxyethyl phosphonate (Dipterex) 0-ethyl 0-p-cyanophenyl phenylphosphonothioate (Surecide) 0-ethyl 0-p-nitrophenyl phenylthiophosphonate (EPN) 0,0-dipropyl 0-4-methylthiophenylphosphate (Propaphos) 0,0-dimethyl S-phthalimidomethyl dithiophosphate (Imidan) 0,0-dimethyl 0-dichlorovinyl phosphate (DDVP) 0,0-dimethyl S-(N-methylcarbamoylmethyl) dithiophosphate (dimethoate) 0,0dimethyl S-( I ,2-dicarbethoxyethyl) dithiophosphate (malthon) I-Naphthyl N-methylcarbamate (NAC) m-Tolyl N-methylcarbamate (MTMC) 2-Isopropoxyphenyl N-methylcarbamate (PHC) Ethyl N-(diethyl-dithiophosphorylacetyl)-N-methylcarbamate (Mecarbam) 3,4-Xylyl N-methylcarbamate (MPMC) 2-s-Butylphenyl N-methylcarbamate (BPMC) 2-Isopropylphenyl N-methylcarbamate (MIPC) 2-Chlorophenyl Nmethylcarbamate (CPMC) 3,5-Xylyl N-methylcarbamate (XMC) 2-(1,3-Dioxolan-2-yl) phenyl N-methylcarbamate (Dioxacarb) 3-t-Butylphenyl N-methylcarbamate (Terbam) 4- Diallylamino-3, 5-dimethylphenyl N-methylcarbamate (APC) S-methyl-N-(methylcarbamoyloxy) thioacetoimidate (Methomil) N-(2-methyl-4-chlorophenyl)-N,N-dimethylformamidine hydrochloride (chlorophenamidine) 1,3-bis(Carbamoylthio)-2-(N,N-dimethylamino)-propane hydrochloride (Cartap) Diisopropyl- 1 ,3-dithiolan-2-ylidine malonate (Isoprothiolan) N- [ [(4-chlorophenyl)aminolcarbonyl] -2,6-difluorobenzamide (Diflubenzuron) 0,0-dimethyl-S- [2-(isopropylthio)ethyl]phosphorodithioate (Isothioate) 0,0-diethyl-S-[2-(ethylthio)ethyll-phosphorodithioate (Disulfoton) 2 3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbamate (Carbofuran) Example 1.

2 - Methylimino - 3 - phenyl - 5 - isopropyltetrahydro - 1,3,5 - thiadiazin 4 - one (compound No. 66).

In 50 ml of benzene, were dissolved 3.4 g (0.02 mole) of N - isopropyl - N chloromethylcarbamoyl chloride and 3.3 g (0.02 mole) of 1 - methyl - 3 - phenyl thiourea. The resulting solution was heated under reflux with stirring for 2 hours.

After cooling, the precipitated crystals were collected by filtration, washed with benzene and dissolved in 200 ml of water. The resulting aqueous solution was admixed with 20 ml of saturated aqueous sodium carbonate solution and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated under reduced pressure to obtain crystals which were recrystallized from isopropyl alcohol. M.p. 174 - 1760C.; yield 2.1 g (40 /O).

NMR(CDC13) : 1.19 (d. 6H), 3.00 (S. 3H), 4.42 (S. 2H), 4.3()-4.80 (m. IH), 7.e 7.6 (m. 5H) Example 2.

2 - p - Tolylimino - 3 - methyl - 5 - t - butyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 72):

In 50 ml of toluene, were dissolved 3.7 g (0,02 mole) of N-t-butyl - N chloromethylcarbamoyl chloride and 3.6 g (0.02 mole) of I - methyl- 3 - p tolylthiourea. The resulting solution was heated under reflux for 2 hours. The precipitated crystals were collected by filtration and washed with acetone (m.p. 189 - 1900C. decomp.). The crystals were dissolved in 100 ml of water, admixed with 10 ml of a 20% sodium hydroxide solution, and extracted with 50 ml of benzene.

The crystals obtained on removal of the benzene under vacuum were recrystallized from isopropyl acohol.

Yield 4.3 g (73%); m.p. 113-115 C.

NMR(CDCl3)#: 1.48 (S. 9H, 2.30 (S. 3H), 3.35 (S. 3H), 4.48 (S. 2H), 6.65-7.25 (m.

4H) In a similar manner, 2 - (2 - methyl - 4- chloro) - phenylimino - 3 methyl - 5 - isopropyl - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No.

67):

was obtained from 3.4 g of N - isopropyl - N - chloromethyl - carbamoyl chloride and 4.2 g of 1 - methyl - 3 - (2 - methyl - 4 - chloro)phenylthiourea. m.p. 9192 C.; yield 3.2 g. NMR(CDCl)#: 1.20 (d. 6H), 2.10 (S. 3H), 3.45 (S. 3H), 4.30 (S.

2H), 4.45 - 4.95 (m, 1H), 6.55 - 7.20 (m. 3H) Example 3.

2 - t - Butylimino - 3 - phenyl - 5 - t - butyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 77):

In 50 ml of acetone, were dissolved 3.7 g (0.02 mole) of N - t - butyl - N chloromethylcarbamoyl chloride and 3.9 g (0.02 mole) of 1 - t - butyl - 3 phenylthiourea. While stirring, 2.8 g of powdered potassium carbonate was added to the resulting solution and heated under reflux for 2 hours. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried, and concentrated under reduced pressure. The crystals obtained were recrystallized from isopropyl alcohol. Yield 4.1 g (66%); m.p. 133 134 C.

NMR(CDCl3) b: 1.10) (S. 9H), 1.46 (S. 9H), 4.60 (S. 2H), 7.0 -- 7.4 (m. 5H) Example 4 2 - Ethylimino - 3 - o - tolyl - 5 - t - butyl - tetrahydro - 1,3,5 thiadiazine - 4 - one (compound No. 80):

In 50 ml of benzene, were dissolved 3.7 g (0.02 mole) of N - t - butyl - N chloromethylcarbamoyl chloride and 3.8 g of 1 - ethyl - 3 - 0 - tolythiourea. While stirring, 8 g of a 20% sodium hydroxide solution was added to the above solution and stirring was continued for further 4 hours at 300 to 500 C. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water and dried. The crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol. Yield 3.8 g (63%); m.p 157 l580C.

Example 5.

2 - Phenylimino - 3 - phenyl - 5 - t - butyl - tetrahydro - 1,3,5 - thiadiazin 4 - one (compound No. 78):

In a mixture of 50 ml benzene and 10 ml of dimethyl sulfoxide, were dissolved 3.7 g (0.02 mole) of N - t - butyl - N - chloromethylcarbamoyl chloride and 4.6 g of 1,3-diphenylthiourea. While stirring at room temperature, 6.1 g of 1,8 - diazabicyclol5,4,0] - 7 - undecene was added to the above solution and stirring was continued for further 5 hours. The reaction mixture was poured into water and extracted with benzene. The benzene layer was washed with water and dried. The crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol. Yield 4.4 g (65%); m.p. 142 -- 143"C.

Example 6.

2 - Isopropylimino - 3 - isopropyl - 5 - methyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 1):

To 2.8 g (0.02 mole) of N - methyl - N - chloromethylcarbamoyl chloride dissolved in 50 ml of benzene, was added 3.2 g (0.02 mole) of 1,3-diisopropyl thiourea. The mixture was heated under retlux with stirring for 2 hours. After cooling, 10 g of a 30% potassium hydroxide solution and 50 ml of benzene were added to the mixture and the mixture was shaken thoroughly. The separated benzene layer was washed with water, dried, and the benzene was distilled off under vacuum. The crystals thus obtained were recrystallized from ether. Yield 3.0 g (66%); m.p. 76 - 77 C.

NMR(CDCl3)#: 1.15 (d. 6H), 1.40 (d. 6H), 3.10 (S. 3H), 4.45 (S. 2H), 4.50 - 4.80 (m.

IH), 3.30 -- 3.80 (m. I H) Example 7.

2 - Ethylimino - 3,5 - diethyl - tetrahydro - 1,3,5 - thadiazin - 4 - one (compound No. 7):

To a mixture of 3.1 g (0.02 mole) of N - ethyl - N - chloromethylcarbamoyl chloride and 2.6 g (0.02 mole) of 1,3-diethylthiourea dissolved in 50 ml of benzene, was added with stirring at room temperature 8 g of a 20% sodium hydroxide solution. After stirring for 5 hours, the reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried and the benzene was distilled off under vacuum. The oily substance thus obtained was crystallized from ether. Yield 2.8 g (66 %); m.p. 68 - 70 C.

NMR(CDCl3)#: 1.20 (t. 9H), 3.20 - 3.70 (m. 4H), 3.75 - 4.10 (q. 2H), 4.40 (S. 2H) Example 8.

2 - Isopropylimino - 3 - methyl - 5 - isopropyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 18):

In 50 ml of benzene, were dissolved 3.4 g (0.02 mol) of N - isopropyl - N chloromethylcarbamoyl chloride and 2.6 g (0.02 mole) of I - isopropyl - 3 methylthiourea. The solution was heated under reflux for 2 hours. After cooling the precipitated crystals (m.p. 198-200 C. decomp.) were collected by filtration, washed with a small quantity of acetone, again dissolved in 100 ml of water, admixed with 10 ml of a 30X potassium hydroxide solution, and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation. The crystals thus obtained were recrystallized from ether.

Yield 3.8 g (83%).

NMR(CI:)CI3) a 1.10 (d. 6H), 1.16 (d. 6M), 3.20 (S. 3H), 4.33 (S. 2H), 4.40-4.85 (m.

IH), 3.30 -- 3.70 (m. IH) Example 9.

2 - Methylimino - 3 - methyl - 5 - t - butyl - tetrahydro - 1,3,5 - thiadiazin 4 - one (compound No. 31):

In 50 ml of toluene, were dissolved 3.7 g (0.02 mole) of N - t - butyl - N chloromethylcarbamoyl chloride and 2.0 g (0.02 mole) of 1,3-dimethylthiourea.

The solution was heated under reflux with stirring for one hour. After cooling, the precipitated crystals (m.p. > 220 C decomp.) were collected by filtration, washed with a small quantity of acetone, dissolved again in 100 ml of water, admixed with 10 ml of a 20% sodium hydroxide solution, and extracted with 50 ml of benzene.

The benzene layer was dried and concentrated under reduced pressure to obtain 3.5 g (83% yield) of crytsls melting at 51-52 C.

NMR(CDCl3)#: 1.47 (S. 9H) 3.03 (S. 3H), 3.14 (S. 3H), 4.53 (S. 2H) Example 10.

2 - t - Butylimino - 3 - benzyl- 5 - t - butyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 47):

In 50 ml of xylene, were dissolved 3.7 g (0.02 mole) of N - t - butyl - N chloromethylcarbamoyl chloride and 4.4 g (0.02 mole) of 1 - t - butyl - 3 - benzylthiourea. To the solution, while being stirred at room temperature, was added 8 g of a 30 potassium hydroxide solution. The mixture was stirred for further 4 hours while heating at 30 to 500 C. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation. The oily substance thus obtained was crystallized from ether. Yield 4.5 g (68%); m.p. 75 -- 76"C.

Example 11.

2 - Methylimino - 3 - methyl - 5 - benzyl - tetrahydro - 1,3,5 - thiadiazin 4 - one (compound No. 54):

A mixture of 4.4 g (0.02 mol) of N - benzyl - N - chloromethylcarbamoyl chloride and 2.0 g (0.02 mole) of 1,3-dimethylthiourea was dissolved in 50 ml of ethyl alcohol and heated under reflux with stirring for 2 hours. After addition of 20 ml of a saturated aqueous potassium carbonate solution, the mixture was extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation under reduced pressure to obtain 4.0 g of crude crystals which were recrystallized from ether. Yield 3.2 g (63%); m.p. 93 -- 95"C.

Example 12 2 - t - Butylimino - 3 - methyl - 5 - (1,1,3,3 - tetramethyl)- butyl ID benzene layer was washed with water, dried, and the benzene was removed by distillation under reduced pressure. The oily substance thus obtained was crystallized from ether. Yield 5.1 g (82%); m.p. 91 - 930C.

NMR(CDC13) S: 0.97 (S. 9H), 1.20 (S. 9H), 1.50 (S. 6H), 1.90 (S. 2H), 3.18 (S. 3H), 4.54 (S. 2H) Example 13.

2 - s - Butylimino - 3H - 5 - t - butyl - tetrahydro - 1,3,5 - thiadiazin - 4 one (compound No. 107):

To 1.4 g (0.01 mole) of s-butylthiourea dissolved in 20 ml of acetone, was added 8 g of a 15% potassium hydroxide solution. The the resulting mixture, was added dropwise 1.9 g of N - chloromethyl - N - t - butylcarbamoyl chloride with stirring at room temperature. After stirring for 30 minutes, the reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was dried and concentrated to obtain crude crystals which were recrystallized from ether-isopropyl alcohol. There were obtained 1.6 g (63% yield) of crystals melting at 98 -- 100"C.

Example 14.

2 - Imino - 3H - 5 - t - butyl - tetrahydro - 1,3,5 - thiadiazin - 4(3H) - one (compound No. 109):

To a suspension of 0.8 g (0.01 mol) of thiourea and 8 g of a 15% potassium hydroxide solution in 50 ml of benzene, was added dropwise 1.9 g (0.01 mole) of N- chloromethyl - N- t - butylcarbamoyl chloride with stirring at room temperature. After stirring for one hour at room temperature, the crystals formed were collected by filtration and recrystallized from chloroform to obtain 0.75 g (41% yield) of crystals melting at 123 -- 125"C.

Example 15.

2 - Methylimino - 3 - methyl - 5 - phenyl - tetrahydro - 1,3,5 - thiadiazin 4 - one (compound No. 115):

In 50 ml of benzene, were dissolved 2.1 g (0.01 mole) of N - chloromethyl N - phenylcarbamoyl chloride and 1.0 g (0.01 mole) of 1,3-dimethylthiourea. The resulting solution was heated under reflux with stirring for 3 hours. After cooling, the benzene layer was removed from the reaction mixture by decantation. The residual layer was washed with a small quantity of benzene. The residue (hydrochloride, m.p. 168 -- 170"C. decomp.) was dissolved in water, admixed with 10 ml of a 10% (W/W) aqueous sodium hydroxide solution and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation under reduced pressure to obtain crude crystals which were recrystallized from isopropyl acohol. Yield 1.3 g (51%); m.p. 68 - 70 C.

NMR(CDCl3)#: 3.15 (S. 3H), .30 (S. 3H), 4.80 (S. 2H), 7.33 (S. 5H) Example 16.

2 - Isopropylimino - 3 - methyl - 5 - phenyl tetrahydro - 1,3,5 - thiadiazin4-one (compound No. 118):

In 50 ml of toluene, were dissolved 2,1 g (0.01 mole) of N-chloromethyl - N phenylcarbamoyl chloride and 1.3 g (0.01 mole) of I - isopropyl - 3 methylthiourea. To the solution, was added with stirring at room temperature 4 ml of a 20% (W/W) aqueous sodium hydroxide solution and the mixture was stirred for 6 hours. The reaction mixture was poured into water and extracted with 50 ml of benzene. The benzene layer was washed with water, dried and concentrated to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 1.3 g (50%); m.p. 72 - 73.5 C.

NMR(CDCl3)#: 1.15 (d. 6H), 3.29 (S. 3H), 3.25-3.85 (m. 1H), 4.73 (S. 2H), 7.28 (S. 5H) Example 17 2 - Isopropylimino - 3 - isopropyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 144):

In 50 ml of benzene, were dissolved 2.1 g (0.01 mole) of N - chloromethyl N - phenylcarbamoyl chloride and 1.6 g (0.01 mole) of 1,3-diisopropylthiourea.

The solution was heated under reflux with stirring for 2 hours. The crystals which were formed were collected by filtration. The crystals (hydrochloride, m.p. 188190 C. decomp.) were washed with a small quantity of cold acetone, dissolved in water, admixed with 2.8 g of powdered sodium carbonate, and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation to obtain crude crystals which were recrystallized from isopropyl acohol. Yiled 1.8 g (62%); m.p. 92 - 94 C.

NMR spectrum (CDCl3)#: 1.15 (d. 6H), 1.49 (d. 6H), 3.25-3.68 (m. 1H), 4.82 4.99 (m. 1H), 4.75 (S. 2H), 7.20 (S. 5H).

IR spectrum (KBr): #c = 0 1660 cm-'.

Example 18.

2 - t - Butylimino - 3 - isopropyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No 145):

In a mixture of 50 ml of acetone and 10 ml of dimethylformamide, were dissolved 2.1 g (0.01 mole) of N - chloromethyl - N - phenylcarbamoyl chloride and 1.7 g (0.01 mole) of 1 - isopropyl - 3 - t - butylthiourea. To the solution, while stirring at room temperature, was added 4 ml of a 30% (W/W) aqueous potassium hydroxide solution and the mixture was stirred for further 5 hours. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol. Yield 2.0 g (65 ""); m.p.

104 - 106 C.

NMR(CDCl3)#: 1.33 (S. 9H), 1.45 (d. 6H), 4.70 (S. 2H), 4.32-5.00 (m. 1H), 7.30 (S.

5H) Example 19.

2 - Isopropylimino - 3 - isobutyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 149):

In a mixture of 50 ml of tetrahydrofuran and 10 ml of dimethyl sulfoxide, were dissolved 2.1 g (0.01 mole) of N - chloromethyl - N - phenylcarbamoyl chloride and 1.7 g (0.01 mol) of I - isopropyl - 3 - isobutylthiourea. To the solution, while stirring at room temperature, was added 2.1 g of triethylamine and the mixture was stirred for further 6 hours. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol. Yield 2.4 g (78%); m.p. 80 -- 820C.

NMR(CDCl3) b: 0.90 (d. 6H), 1.15 (d. 6H), 1.70 -- 2.30 (m. IH), 3.35 - 3.75 (m.

1H), 4.05 (d. 2H), 4.75 (S. 2H) 7.30 (S. 5H) Example 20 2 - t - Butylimino - 3 - cyclohexyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 155):

In 50 ml of ether, were dissolved 2.1 g (0.01 mole of N - chloromethyl - N phenylcarbamyl chloride and 2.1 g (0.01 mole) of I - cyclohexyl - 3 - t - butylthiourea followed by 1.6 g of pyridine. The resulting solution was stirred for 4 hours at room temperature. The reaction mixture was poured into water and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain an oily substance which was crystallized from isopropyl alcohol. Yield 1.6 g (45%); m.p. 86 -- 89"C.

NMR(CDC13) : 1.35 (S. 9H), 1.0 -- 2.5 (m. 11H), 4.75 (S. 2H), 7.33 (S. 5H) Example 21.

2 - Benzylimino - 3 - methyl - 5 - phenyl - tetrahydro - 1,3,5 - thiadiazin 4 - one (compound No. 121):

In 20 ml of a 6% (W/W) aqueous potassium hydroxide solution, was suspended 1.8 g (0.01 mole) of I - methyl - 3 - benzylthiourea. To the suspension, was added with stirring. at room temperature 2.1 g of N - chloro - methyl - N - phenylcarbamoyl chloride and the mixture was vigorously stirred for one hour at room temperature. The reaction mixture was poured into water and extracted with 100 ml of benzene The benzene layer was washed with water, dried, and concentrated to obtain an oil substance which was crystallized from isopropyl alcohol. Yield 2.0 g (63%); m.p. 90 -- 92"C.

NMR(CDCl3) a: 3.35 (S. 3H), 4.50 (S. 2H), 4.65 (S. 2H), 7.0 -- 7.5 (m. 1QH) Example 22.

2 - n - Octylimino - 3 - methyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 122):

In ethyl alcohol, were dissolved 2.1 g (0.01 mole of N - chloromethyl - N phenylcarbamoyl chloride and 2.0 g (0.01 mole) of I - methyl - 3 - n octylthiourea. The solution was heated under reflux with stirring for 3 hours. After cooling, the reaction mixture was poured into water, admixed with 5 ml of a 20% (W/W) aqueous sodium hydroxide solution, and extracted with 100 ml of benzene.

The benzene layer was washed with water, dried and concentrated to obtain a viscous oily substance which was dissolved in 6N hydrochloric acid and freed from the insoluble matter by extraction with benzene. The aqueous layer was made slightly alkaline by addition of a 20% (W/W) aqueous sodium hydroxide solution and extracted with 50 ml of benzene. The benzene layer was washed wit'n water, dried, and concentrated to obtain a viscous oily substance. Yield 1.2 g (36%); n2D 1.5551.

Example 23.

2 - s - Butylimino - 3,5 - diphenyl - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 163):

In a mixture of 50 ml of ethyl acetate and 10 ml of dimethyl sulfoxide, were dissolved 2.1 g (0.01 mole) of N - chloromethyl -. N - phenylcarbamoyl chloride and 1.9 g (0.01 mole) of 1 - s - butyl - 3 - phenylthiourea. To the solution, was added 1. 1 g of powdered sodium carbonate and the mixture was stirred for 3 hours at 50"C. The reaction mixture was poured into water and extracted with 50 ml of ethyl acetate. The ethyl acetate layer was washed with water, dried, and concentrated to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 1.9 g (57%); m.p. 134 - 135.50C.

NM R(CDCI3) 8: 0.5 - 1.5 (m. 8H), 3.0 - 3.5 (m. 1 H), 4.85 (S. 2H), 7.25 (S. iOH) Example 24.

2 - (2 - Methyl)phenylimino - 3 - methyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No 124):

In 50 ml of benzene, were dissolved 2.1 g (0.01 mole) of N - chloromethyl N - phenylcarbamoyl chloride and 1.8 g (0.01 mole) of 1 - methyl - 3 - o - tolylthiourea. To the solution, while stirring at room temperature, was added 3.1 g of 1,8 - diazabicyclo - [5,4,0] - 7 - undecene and the mixture was stirred for 4 hours.

The reaction mixture was poured into water and extracted with 100 ml of benzene.

The benzene layer was washed with water, dried, and concentrated to obtain crude crystals which were recrystallized from isopropyl alcohol. Yield 2.0 g (63%); m.p.

113 - 1140C.

NMR(CDCI3) b: 2.18 (S. 3H), 3.50 (S. 3H), 4.68 (S. 2H), 7.0 -- 7.5 (m. 9H) Example 25.

2 - Methylimino - 3 - (2 - methyl - 4 - chloro)phenyl - 5 - phenyl tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 166):

In a mixture of 10 ml of benzene and 10 ml of tetrahydrofuran, were dissolved 1.4 g (1/150 mole) of N - chloromethyl - N - phenylcarbamoyl chloride and 1.4 g (1/150 mole) of l-methyl-3-(2-methyl-4-chloro)-phenylthiourea. To the solution was added with stirring, 5.5 g of a 10% (W/W) aqueous sodium hydroxide solution, and the mixture was vigorously stirred for 4 hours, while maintaining the reaction temperature at 400 C. After completion of the reaction, the benzene layer was washed with water and concentrated to obtain an oily mixture of 2 - methylimino3 - (2 - methyl - 4 - chloro) - phenyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one and 2 - (2 - methyl - 4 - chloro)phenylimino - 3 - methyl 5 - phenyl - tetrahydro - 1,3,5 - thiadiazin - 4 - one.

The compound No. 166 could be separated from the above mixture in the following manner.

The above oily mixture was dissolved in 3N hydrochloric acid and the insoluble matter was removed by washing with ethyl acetate. The aqueous layer was made slightly alkaline to precipitate crystals which were recrystallized from isopropyl alcohol-n-hexane to obtain 1.2 g (52% yield) of the compound No 166 melting at 121 - 1230C.

NMR(CDC13) S: 2.18 (S. 3H), 3.07 (S. 3H: =N--CH,), 4.92 (S. 2H) Example 26.

2 - Methylimino - 3 - methyl - 5 - (p - chlorophenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 188):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N - chloromethyl N - (p - chlorophenyl) - carbamoyl chloride and 1.0 g (0.01 mole) of 1,3 dimethylthiourea. The solution was heated under reflux for one hour. The crystals which were formed were collected by filtration and washed with acetone. The resulting white crystals (hydrochloride, m.p. 205"C) were dissolved in water, admixed with 5 ml of a 20% sodium hydroxide solution, shaken thoroughly, and extracted with benzene. The crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol to obtain 1.6 g (60% yield) of crystals melting at 98 - 1000C.

Example 27.

2 - Isopropylimino - 3 - methyl - 5 - (p - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 189):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N - chloromethyl N - (p-chlorophenyl) - carbamoyl chloride and 1.3 (0.01 mole) of 1 - isopropyl 3 - methylthiourea. To the solution was added dropwise with stirring, 8 ml of a 10% sodium hydroxide solution, and the mixture was further stirred for 4 hours at 400 C.

The reaction mixture was poured into water and extracted with benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation to obtain crystals which were recrystallized from isopropyl alcohol.

There were obtained 2.4 g (82% yield of crystals melting at 106 - 108 C.

NMR(CDCl3)#: 1.18 (d. 6H), 3.32 (S. 3H), 3.55 (m. 1H) 4.80 (S. 2H), 7.25 (S. 4H) In a manner similar to that described above, 2.3 g (0.01 mole) of i -isopropyl 3 - t - octylthiourea and 2.7 g (0.01 mole) of N-chloromethyl - N - m - trifluoromethyl - phenylcarbamoyl chloride were treated to obtain 2 - t - octylimino - 3 isopropyl - 5 - (m - trifluoromethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 one (compound No. 266) as an oily substance:

n 24 1.5089 NMR(CDCl3) a: 4.70 (s. 2M, - N-CM3-S-) Example 28.

2 - t - Butylimino - 3 - isopropyl - 5 - (p - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 196):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N - chloromethyl N - (p - chlorophenyl) - carbamoyl chloride and 1.7 g (0.01 mole of 1 -isopropyl 3 - t - butylthiourea. After addition of 8 ml of a 15% potassium hydroxide solution, the mixture was allowed to react by heating at 400 to 500 C. with stirring for 4 hours, The reaction mixture was poured into water and extracted with benzene. The benzene layer was washed with water, dried, and the benzene was removed by distillation to obtain crude crystals which were recrystallized from ethanol. There were obtained 2.0 g (62% yield) of crystals melting at 123 - 1250C.

Example 29.

2 - t - Butylimino - 3 - benzyl - 5 - (p - chlorophenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 204):

In 50 ml of toluene, were dissolved 2.4 g (0.01 mole) of N - chloromethyl - N (p - chlorophenyl) - carbamoyl chloride and 2.2 g (0.01 mole of 1 - t - butyl - 3 benzylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 400 to 500 C. with stirring for 4 hours.

The reaction mixture was washed with water and the toluene layer was dried and freed from the toluene by distillation to obtain crude crystals which were recrystallized from isopropyl acohol. There were obtained 2.8 g (7.3% yield) of crystals melting at 87 - 89 C.

Example 30.

2 - t - Butylimino - 3 - ethyl - 5 - (m - chlorophenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 216):

In 50 ml of tetrahydrofuran, were dissolved 2.4 g (0.01 mole) of N chloromethyl - N - (m - chlorophenyl) - carbamoyl chloride and 1.6 g (0.01 mole) of'l - ethyl - 3 - t - butylthiourea. After addition of 8 ml of a 15% potassium hydroxide solution, the mixture was allowed to react by heating at 40 to 500C with stirring for 4 hours. The reaction mixture was poured into water and extracted with benzene. The benzene layer was dried and concentrated to obtain a viscous oily substance. n20 1.5683 NMR(CDCI3) S: 3.90(q. 2M, - N-C2K5) 4.70 (s. 2M, -N-CM2-S-) Example 31.

2 - t - Butylimino - 3 - s - butyl - 5 - (m - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 225):

In 50 ml of xylene, were dissolved 2.4 g (0.01 mole) of N - chloromethyl - N (m - chlorophenyl) - carbamoyl chloride and 1.8 g (0.01 mole) of I - s - butyl - 3 t - butylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40500 C. with stirring for 4 hours. The reaction mixture was washed with water, dried, and dry gaseous hydrogen chloride was introduced into this xylene solution at room temperature until no more crystals had been precipitated. The crystals were collected by filtration and washed with acetone. The crystals (hydrochloride, m.p. 186"C. decomp.) were suspended in water, admixed with 10 ml of a 15% potassium hydroxide solution, shaken well, and extracted with benzene. The benzene layer was dried and freed from the benzene by distillation to obtain 1.9 g (60% yield) of white crystals melting at 75 -- 76"C.

Example 32.

2 - Isopropylimino - 3 - isopropyl - 5 - (o - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 244):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N - chloromethyl N - (o - chlorophenyl)-- carbamoyl chloride and 1.6 g (0.01 mole) of 1,3diisppropylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 500 to 600 C. with stirring for 4 hours.

The reaction mixture was washed with water, dried, and freed from the benzene by distillation to obtain crude crystals which were recrystallized from isopropyl alcohol to obtain 1.8 g (56% yield) of crystals melting at 95 - 960C.

NMR(CDCI3) : 1.15 (d. 6H), 1.45 (d. 6H), 4.68 (s. 2H), 3.50 (m. IH), 4.73 (m. IH), 7.15 (m. 4H) The above procedure was followed using 1.7 g (0.01 mole) of 1 - isopropyl 3 - t - butylthiourea to obtain white crystals (m.p. 88 - 89"C) of 2 - t butylimino - 3 - isopropyl - 5 - (o - chlorophenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 245):

Yield 2.3 g (70%). The crystals were dissolved in benzene and gaseous hydrogen chloride was introduced into the solution. The precipitated crystals were collected by filtration and washed with acetone to obtain crystalline hydrochloride melting at 201"C. (decomp.).

In a similar manner, 1.7 g (0.01 mole) of 1 - isopropyl - 3 - s - butylthiourea and 2.2 g (0.01 mole) of N-chloromethyl - N - (p - fluorophenyl) - carbamoyl chloride were allowed to react to yield crystals melting at 81 - 820C. The crystals gave single spot on a thin-layer chromatogram using a hexane-acetone mixture (8 2) as developing solvent. However, the NMR spectrum revealed that the crystals were approximately 1: I mixture of the compounds No. 361 and No. 362: 2 - Isopropylimino - 3 - s - butyl - 5 - (p - fluorophenyl) - tetraahydro 1,3,5 - thiadiazin - 4 - one:

2 - s - Butylimino - 3 - isopropyl - 5 - (p - fluorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one:

Example 33.

2 - Methylimino - 3 - methyl - 5 - (p - fluorophenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one hydrochloride (compound No. 277):

In 50 ml of benzene, were dissolved 1.0 g (0.01 mole) of 1,3-dimethylthiourea and 2.2 g (0.01 mole) of N-chloromethyl-N-(p-flurophenyl)-carbamoyl chloride.

The solution was heated under reflux with stirring for one hour. The oily substance obtained on removal of the benzene by distillation was dissolved in acetone and the precipitated crystals were collected by filtration and washed with acetone to obtain 2.1 g (85% yield) of white crystals of the hydrochloride melting at 221"C.

(decomp.). A portion (1 g) of the crystals was dissolved in 20 ml of water, admixed with 5 ml of a 10% sodium hydroxide solution, shaken thoroughly, and extracted with benzene,. The benzene layer was dried and concentrated to obtain crystals of free base melting at 105-1060C.

In a similar manner, 1.7 g (0.01 mole) of l-isopropyl-3-t-butylthiourea was reacted with 2.2 g (0.01 mole) of N-chloromethyl-N-(p-fluorophenyl)-carbamoyl chloride to obtain 2-t-butylimino-3-isopropyl 5-(p-fluorophenyl)-tetrahydro-1,3,5- thiadiazin-4-one (compound No. 282):

in the form of hydrochloride melting at 160--1950C. Yield 2.8 g (80%). The crystals were suspended in 20 ml of water and treated in a manner similar to that described above to obtain white crystals of the free bas melting at 109--1 100C. (isopropanol).

Yield 2.0 g (63%).

Example 34.

2 - Isopropylimino - 3 - allyl - 5 - (m - chlorophenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 217):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(m chlorophenyl)-carbamoyl chloride and 1.58 g (0.01 mole) of I-allyl-3-isopropylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution to the solution, the mixture was allowed to react by heating at 400 to 500 C. with stirring for 4 hours.

The reaction mixture was washed with water, dried, and concentrated to obtain a viscous oily substance (n'D 1.5857) in a yield of 80%.

The above oily substance was dissolved in benzene, and gaseous hydrogen chloride was introduced into the solution to obtain hydrochloride melting at 1790C.

(decomp.).

Example 35.

2 - t - Butylimino - 3 - isopropyl - 5 - (m - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 221):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(mchlorophenyl)-carbamoyl chloride and 1.74 g (0.01 mole) of l-isopropyl-3-t- butylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 400 to 500C. with stirring for 4 hours.

The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol to obtain 1.5 g (45%) yield of white crystals having a melting point of 113-115 C. The crystals were dissolved in benzene, and gaseous hydrogen chloride was passed into the solution to obtain hydrochloride melting at 1520C. (decomp.).

Example 36.

2 - Cyclohexylimino - 3 - isopropyl - 5 - (o - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 252):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(ochlorophenyl)-carbamoyl chloride and 2.0 g (0.01 mole) of l-isopropyl-3-cyclohexylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40 to 50 C. with stirring for 4 hours.

After completion of the reaction, the benzene layer was washed with water, dried, and concetrated to obtain a viscous oily substance which was crystallized from isopropyl acohol-n-hexane (1:1) to obtain white crystals melzing at 123-125 C. in a yield of 22.5%.

Example 37.

2 - Ethylimino - 3 - phenyl - 5 - (o - chlorophenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 256):

In 50 ml of benzene, were dissolved 2.4 g (0.01 mole) of N-chloromethyl-N-(ochlorophenyl)-carbamoyl chloride and 1.8 g (0.01 mole) of l-ethyl-3-phenyl- thi6urea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 400 to 500 C. with stirring for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl alcohol-n-hexane (1:1) to obtain 0.8 g (14 /O yield) of white crystals melting at 77-790C.

Example 38.

2 - Isopropylimino - 3 - isopropyl - 5 - (m - trifluoromethylphenyl) tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 265):

In 50 ml of benzene, were dissolved 2.7 g (0.01 mole) of N-chloromethyl-N-(mtrifluoromethyl-phenyl)-carbamoyl chloride and 1.6 g (0.01 mole) of 1,3diisopropylthiourea. After addition of 8 ml of a 10% sodium hydroxide solution, the mixture was allowed to react by heating at 40 to 500C. with stirring for 4 hours.

After completion of the reaction, the benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance which was crystallized from isopropyl acohol-n-hexane (1:1) to yield 1.3 g (36% yield) of white crystals melting at 67-68 C.

Example 39.

2-t-Butylimino-3-isopropyl-5-(p-tolyl)tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 318):

In 10 ml of tetrahydrofuran, was suspended 1.0 g (0.0028 mole) of 1,3,5-tris(ptolyl)-hexahydro-s-triazine. The resulting suspension was added dropwise with stirring to 5 ml of ice-cooled benzene containing 0.9 g (0.0042 mole) of trichloromethyl chloroformate. After completion of the dropwise addition, the mixture was stirred for one hour at room temperature. To the admixture, was added 20 ml of benzene containing 1.4 g (0.0083 mole) of l-isopropyl-3-t-butylthiourea.

After addition of 7 ml of a 10% sodium hydroxide solution, the mixture was stirred for 4 to 6 hours at 400C to 500 C. The reaction mixture was washed with water, dried, and freed from the benzene by distillation. The crude product thus obtained was recrystallized from isopropyl alcohol to obtain 1.2 g (45% yield) of white crystals melting at 118120 C.

NMR(CDCL3) a 4.75 (s. 2H), 4.70 (m. I 2.35 (s. 3H), 1.47 (d. 6H), 1.33 (s. 9H) Example 40.

2 - Benzylimino - 3 - benzyl - 5 - (p - tolyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 321):

(s. 2H, N-CM3-), 4.78 (s. 2H), 4.50 (s. 2H, N-CM3-), 2.32 (s. 3H).

In 10 ml of tetrahydrofuran, was suspended 1.0 g (0.0028 mole) of 1,3,5-tris(ptolyl)-hexahydro-s-triazine. The suspension was added dropwise with stirring at room temperature to 5 ml of benzene containing 0.9 g (0.0042 mole) of trichloromethyl chloroformate. Thereafter, the mixture was stirred for one hour at room temperature. To the mixture was added 2.1 g (0.0083 mole) of 1,3 bis(benzyl)thiourea dissolved in 20 ml of benzene, followed by 7 ml of a 10% sodium h A solution of 2.4 g (0.0067 mole) of 1,3,5-tris(o-tolyl)-hexahydro-s-triazine in 10 ml of tetrahydrofuran was added dropwise with stirring at room temperature to 10 ml of benzene containing 2.0 g (0.01 mole) of trichloromethyl chloroformate.

Thereafter, the mixture was stirred for 30 minutes at 300 C. To the mixture, was added a solution of 3.2 g (0.02 mole) of l,3-diisopropylthioureain 30 ml of benzene, followed by 16 ml of a 10% sodium hydroxide solution. The mixture was stirred for 4 hours at 40 C., washed with water, dried, and freed from the benzene by distillation. The residula oily substance was admixed with n-hexane and freed from the insoluble matter by filtration. The n-hexane was removed from the filtrate by distillation, leaving behind 3 g (49% yield) of colorless oily substance. nD20 1.5587 NMR(CDCl3)#: 4.77 (m. 1H, N-CH-), 4.52 (s. 2H), 3.48 (m. I H, =N-CH-), 22.3 (s. 3H), 14.9 (d. 6H), 1.17(d. 6H) The above procedure was followed using 1.5 g (0.0042 mole) of 1,3,5-tris(o- tolyl)-hexahydro-s-triazine, 1.3 g (0.0063 mole) of trichloromethyl chloroformate, 3.0 g (0.013 mole) of 1,3-bis(cyclohexyl)-thiourea, and 11 ml of a 10% sodium hydroxide solution to obtain 2.2 g (46% yield of 2 - cyclohexylimino - 3 cyclohexyl - 5 - (o - tolyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No.

307) of the formula:

as colorless oily substance (nD 1.5568).

In a similar manner 1.7 g (0.004 mole) of hexahydro-l,3,5-tris(p-ethylphenyl)-striazine, 1.3 g (0.006 mole) of trichloromethyl chloroformate, 1.3 g (0.012 mole) of I ,3-dimethylthiourea, and 11 ml of a 10% sodium hydroxide solution were used to obtain 0.8 g (24% yield) of 2-methylimino-3-methyl-5-(p-ethylphenyl)-tetrahydro l,3,5-thiadiazin-4-one (compound No. 331) of the formula,

as colorless oily substance (n20 1.5922).

Similarly, 1.7 g (0.004 mole) of hexahydro-1,3,5-tris (p-ethylphenyl)-s-triazine, 1.3 g (0.006 mole) of trichloromethyl chloroformate, 2.2 g (0.012 mole) of Iisopropyl-3-t-butylthiourea, and 11 ml of a 10% sodium hydroxide solution were used to obtain 0.7 g (17% yield) of 2-t-butylimino-3-isopropyl-5-(p-ethylphenyl)tetrahydro-1,3,5-thiadiazin-4-one(compound No. 133) of the formula,

as white crystals (m.p. 70-72 C.).

Similarly, 2.2 g (0.006 mole) of hexahydro-l,3,5-tris(o-ethylphenyl)-s-triazine 1.7 g (0.008 mole) of trichloromethyl chloroformate, 3.1 g (0.0016 mole) of l-sbutyl-3-t-butylthiourea, and 15 ml of a 10% sodium hydroxide solution were used to obtain 2.7 g (47% yield) of 2-t-butylimino-3-s-butyl-5-(o-ethylphenyl)-tetrahydro1 ,3,5-thiadiazin-4-one (compound No. 339) of the formula,

as colorless viscous oily substance (nD 1.5401).

Example 42.

2-t-B utylimino-3-isopropyl-5-(p-methoxyphenyl)-tetrahydro- ,3,5-thiadiazin4-one (compound No. 353):

In 20 ml of tetrahydrofuran, was suspended 2.7 g (0.0067 mole) of 1,3,5-tris-(pmethoxyphenyl)-hexahydro-s-triazin. The suspension was added dropwise with stirring at room temperature to 10 ml of benzene containing 2.0 g (0.01 mole) of trichloromethyl chloroformate, and further stirred for 30 minutes at 300 C. To the mixture, was added a solution of 3.5 g (0.02 mole) of l-isopropyl-3-t-butylthiourea in 30 ml of benzene, followed by 16 ml of a 10% sodium hydroxide solution. The mixture was stirred for 4 hours at 40"C., washed with water, dried and freed from the benzene by distillation. The residual oily substance was admixed with n-hexane and freed from the insoluble matter by filtration. The filtrate was freed from the nhexaned by distillation, leaving behind crude crystals which were recrystallized from isopropyl alcohol to yield 3.4 g (51% yield) of white crystals melting at 99--101.50C.

NMR(CDCI3) : 4.64 (s. 2H), 4.59(m. I H), 3.75 (s. 3H), 1.43 (d. 6H), 1.31 (s. 9H).

Similarly, 2.7 g (0.0067 mole) of 1.3.5-tris-(p-methoxyphenyl)-hexahydro-s- triazine, 2.0 g (0.01 mole) of trichloromethyl chloroformate, 3.8 g (0.02 mole) of l-s- butyl-3-t-butylthiourea, and 16 ml of a 10% sodium hydroxide solution were used to. obtain 1.8 g (26% yield) of 2-t-butylimino-3-s-butyl-5-(p-methoxyphenyl)-tetra hydro-1,3,5-thiadiazin-4-one (compound No. 355) of the formula:

as white crystals melting at 630C.

* NMR(CDCl3) b: 4.70 (s. 2H), 4.36 (q. 1H) 3.75 (s. 3H), 1.9 (m. 2K), 1.47 (d. 3H), 1.32 (s. 9H), 0.92 (t. 3H).

Similarly, 1.4 g (0.0033 mole of 1,3,5-tris(p-methoxyphenyl)-hexahydro-striazine, 1 g (0.005 mole) of trichloromethyl chloroformate, 2.1 g (0.01 mole) of 1isopropyl-3-benzylthiourea, and 9 ml of a 10% sodium hydroxide solution were used to obtain 1.9 g (52% yield) of 2 - isopropylimino - 3 - benzyl - 5 - (p methoxyphenyl)tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 356) of the formula,

as white crystals melting at 1140C.

(s. 2M,N-CM2-), 4.72 (s. 2H), 3.75 (s. 3H), 3.52 (m. I H), 1.09 (d. 6H).

Example 43.

2 - t - Butylimino - 3 - isopropyl - 5 - (o - isopropyl) - phenyl - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 343):

To a solution of 1.4 g (0.003 mole) of 1,3,5-tris(o-isopropyl)phenyl-hexahydro- s-triazine in 20 ml of tetrahydrofuran, was added dropwise with stirring at room temperature 1.0 g of trichloromethyl chloroformate. After 10 minutes of stirring, to the mixture was added a solution of 1.7 g of l-isopropyl-3-t-butylthiourea in 20 ml of benzene, followed by 8 ml of a 15% potassium hydroxide solution. The mixture was stirred for 3 hours at 409 to 500 C. The reaction mixture was poured into water and extracted with 50 ml of benzene. the benzene layer was dried and freed from the benzene by distillation, leaving behind crude crystals which were recrystallized from isopropyl alcohol to yield 1.7 g (52% yield) of white crystals melting at 108--109"C: Example 44.

2 - Isopropylimino - 3 - isopropyl - 5 - (p - bromophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 293):

In 50 ml of benzene, were dissolved 2.8 g (0.01 mole of N-chloromethyl-N-(pbromophenyl)-carbamoyl chloride and 1.6 g of 1,3-diisopropylthiourea. To the solution was added with stirring 4 ml of a 20% sodium hydroxide solution and the mixture was allowed to react at 400 to 500C for 4 hours. The reaction mixture was washed with water, dried, and freed from the benzene by distillation to obtain crude crystals which were recrystallized from isopropyl alcohol to yield 1.6 g (45% yield) of white crystals melting at l21-1220C.

Example 45.

2 - t - Butylimino - 3 - s - butyl - 5 - (4 - ethoxyphenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 368):

A solution of 1.50 g (0.0033 mole) of hexahydro-1,3,5-tris(4-ethoxyphenyl)-s- triazine in 10 ml of tetrahydrofuran was added dropwise with stirring to 10 ml of benzene containing 1.1 g of phosgene. To the mixture was added 1.88 g of 1 -s-butyl- 3-t-butylthiourea followed by a 15% potassium hydroxide solution. The mixture was stirred tor 4 hours at 400 to 500C. The reaction mixture was poured into water and extracted with 50 ml of benzene. the benzene layer was washed with water, dried, and concentrated. The crude crystals thus formed were recrystallized from isopropyl alcohol to obtain 1.7 g (46% yield) of white crystals melting at 66--67"C.

Example 46.

2 - Ethylirnino - 3 - ethyl - 5 - (3,4 - dichlorophenyl) - tetrahydro - 1,3,5 thiadiaiin - 4 - one (compound Nd. 413):

In a conical flask, were placed 2.73 g (0,01 mole) of N,-(3,4-dichlorophenyl)-N- chloromethylearbamoyi chloride, 30 ml of benene, and 1.32 g (0.01 mole) of 1,3 diethylt,hiourea to form a homogeneous solution. To the solution, was added 8 ml of a 10% sodium hydroxide solution and the reactant solution was allowed to react with stirring in a water bath at 400 to 500 C. for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried over anhydrous sodium sulfate, and concentrated. The residual oily substance was crystallized from isopropyl alcohol to obtain 1.4 g (43% yield) of white crystals melting at 86--880C.

Example 47.

2 - Benzylimin - 3 - benzyl - 5 - (3,4 - dichlorophenyl) - tetrahydro 1,3,5 -'thiadiazin -4 -one (compound No. 423):

In a reactor, were placed 2.73 g (0.01 mole) of N-(3,4-dichlorophenyl)-Nchloromethylcarbamoyl chloride, 30 ml of benzene, and 2.56 g (0.01 mole) of 1,3 dibenzylthiourea. To the mixture was added tetra-hydrofuran to form a homogeneous solution To the solution was added 8 ml of a 10% aqueous sodium hydroxide solution, and the reactant mixture was allowed to react with stirring in a water bath at 400 to 50;OC. for 4 hours. After completion of the reaction, the benzene layer was washed with water, and dried over anhydrous sodium sulfate, and gaseous hydrogen chloride was introduced into the benzene layer to obtain the hydrochloride of the intended compound. The hydrochloride was added to a mixture of 10 ml of a 10% aqueous sodium hydroxide solution and 30 ml of benzene to yield 1.5 g (33% yield) of white crystals of the intended compound in the form of free base melting at 118--1200C.

Example 48.

2 - t - Butylimino - 3 - isopropyl - 5 - (3,4 - dichlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No.416):

In a reactor, were placed 2.73 g (0.01 mole) of N-(3,4-dichlorophenyl)-Nchloromethylcarbamoyl chloride, 30 ml of benzene, and 1.74 g (0.01 mole) of 1isopropyl-3-t-butylthourea. To the mixture was added dropwise 8 ml of a 10% aqueous sodium hydroxide solution. The reactant mixture was allowed to react with stirring in a water bath at 400 to 500 C. for 4 hours. The reaction mixture was treated in a manner similar to that in Example 46 to obtain 0.9 g of white crystals melting at 114.5--117.50C.

Example 49.

2 - Isopropylimino - 3 - benzyl - 5 - (3,5 - dichlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 408):

In a reactor were placed 1.37 g (0.005 mole) of N-(3,5-dichlorphenyl)-N chlorornethylcarbamoyl chloride, 1.04 g (0.005 mole) of l-benzyl-3-isopropyl- thiourea, and 20 ml of benzene. After dropwise addition of 4 ml of a 10% aqueous sodium hydroxide solution, the reactant mixture was allowed to react in a water bath at 40 to 500 C. for 2 hours. After completion of the reaction, the benzene layer was washed with water, dried, and gaseous hydrogen chloride was passed through the benzene layer to obtain hydrochloride of the intended compound. The hydrochloride was added to a mixture of 10 ml of 10% aqueous sodium hydroxide solution and 20 ml of benzene to dissolve the liberated free base in benzene. The benzene layer was concentrated and an oily substance obtained as the residue was crystallized from an isopropyl alcohol-n-hexane (1:1 V/V) mixture to obtain 0.8 g (39% yield) of white crystals melting at 9e920C.

Example 50.

2 - Isopropylimino - 3 - allyl - 5 - (3,5 - dichlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No.412):

In a reactor, were placed 2.73 g (0.01 mole) of N-(3,5-dichlorophenyl)-Nchloromethylcarbamoyl chloride, 1.58 g of l-allyl-3-isopropylthiourea, and 30 ml of benzene. To the mixture was added dropwise 8 ml of a 10% aqueous sodium hydroxide solution and the reactant mixture was allowed to react with stirring in a water bath at 400 to 500 C. for 4 hours. After completion of the reaction, the benzene layer was washed with water, dried, and concentrated to leave an oily substance at the residue. The oily substance was purified by silica gel column chromatography to obtain 0.8 g (22.3% yield) of an oily substance (n0l8.s (1.5962).

Example 51.

2 - t - Butylimino - 3 - s - butyl - 5 - (p - ethoxyphenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 368):

A solution of 2.7 g (0.006 mole) of 1,3,5-tris-(p-ethoxyphenyl)-hexahydro-s- triazine in 10 ml of tetrahydrofuran was added dropwise with stirring at room temperature to 10 ml of benzene containing 1.8 g (0.009 mole) of trichloromethyl chloroformate, and the mixture was stirred for further 20 minutes at 40"C. To the mixture was added a suspension of 3.1 g (0.017 mole) of l-s-butyl-3-t-butylthourea in 20 ml of benzene, followed by 15 g of a 10% aqueous sodium hydroxide solution.

The reactant mixture was stirred for 3 hours at 400 C. and thereafter the reaction mixture was washed with water, dried, and freed from the benzene by distillation.

The residual oily substance was mixed with n-hexane and freed from the insoluble matter by filtration. On removal of the n-hexane from the filtrate by distillation, there were obtained crude crystals which were recrystallized from isopropyl alcohol to yield 3.2 g (53% yield) of white crystals melting at 66--670C.

In a similar manner, 2.4 g (0.006 mole) of 1,3,5-tris(2,3-dimethylphenyl)hexahydro-s-triazine, 1.8 g (0.009 mole) trichloromethyl chloroformate, 3.1 g (0.017 mole) l-ethyl-3-cyclohexyl-thiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 3.5 g (61% yield) of 2 - cyclohexylimino - 3 - ethyl 5 - (2,3 - dimethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 382) of the formula,

as white crystals melting at 151--1520C.

Similarly, 2.4 g (0.006 mole) of l,3,5-tris-(2,3-dimethylphenyl)-hexahydro-s- triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.9 g (0.017 mole) of l-isopropyl-3-t-butylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 2.5 g (45% yield) of 2 - t - butylimino - 3 - isopropyl 5 - (2,3 - dimethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 384) of the formula,

as white crystals melting at 91--920C.

Similarly, 1.6 g (0.004 mole) of l,3,5-tris(2,3-dimethylphenyl)-hexahydro-s-tri- azine, 1.2 g (0.006 mole) of trichloromethyl chloroformate, 2.7 g (0.012 mole) of 1benzyl-3-t-butylthiourea, and 11 g of a 10% aqueous sodium hydroxide solution were used to obtain 2.5 g (53% yield) of 2 - t - butylimino - 3 - benzyl - 5 - (2,3 dimethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 386) of the formula,

as colourless oily substance (n2D 1.5769).

Example 52.

2 - Isopropylimino - 3 - methyl - 5 - (p - isopropoxyphenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 370):

A solution of 2.8 g (0.006 mole) of l,3,5-tris-(p-isopropoxyphenyl)-hexahydro- s-triazine in 10 ml of tetrahyrofuran was added dropwise at room temperature to 10 ml of benzene containing 1.8 g (0.009 mole) of trichloromethyl chloroformate and the mixture was stirred for 20 minutes at 400 C. To the mixture was added a suspension of 2.2 g (0.017 mole) of l-methyl-3-isopropylthiourea in 20 ml of benzene, followed by dropwise addition of 15 g of a 10% aqueous sodium hydroxide solution over a period of about one hour. Thereafter, the mixture was stirred for further 2 hours at 50"C. The reaction mixture was washed with water and the remaining benzene layer was intimately mixed with 20 ml of 3N hydrochloric acid to form hydrochloride of the intended compound. The aqueous layer containing the hydrochloride was washed again with fresh benzene, made sufficiently alkaline with an alkali solution, and extracted with benzene. The benzene layer was washed with water, dried, and freed from the benzene by distillation. The residue was recrystallized from isopropyl alcohol to give 1.2 g (23/ yield) of white crystals melting at 112-1 130C.

In a similar manner, 2.8 g (0.006 mole) of 1,3,5-tris(p-isopropoxyphenyl)-hexa- hydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.6 g (0.016 mole) of 1,3-diisopropylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.4 g (24% yield) of 2 - isopropylimino - 3 isopropyl - 5 - (p - isopropoxyphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 372) of the formula,

as white crystals melting at 60-61 0C.

Similarly, 2.8 g (0.006 mole) of l,3,5-tris(p-isopropoxyphenyl)-hexahydro-s- triazine, 1.8 g (0.009 mole) of trichlormethyl chloroformate, 3.0 g (0.016 mole) of 1s-butyl-3-t-butylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.5 g (25% yield) of 2 - t - butylimino - 3 - s - butyl - 5 - (p isopropoxyphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 374) of the formula,

as colorless oily substance (n2D0 1.5402).

Similarly, 2.0 g (0.004 mole) of l,3,5-tris(p-isopropoxyphenyl)-hexahydro-s-tri- azine, 1.2 g (0.006 mole) of trichloromethyl chloroformate, 3.1 g (0.012 mole) of 1,3dibenzylthiourea, and 11 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.5 g (28% yield) of 2 - benzylimino - 3 - benzyl - 5 - (p isopropoxyphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 375) of the formula,

as white crystals melting at 141-1420C.

Example 53.

2 - Isopropylimino - 3 - methyl - 5 - (2,4 - dimethylphenyl) - tetrahydro 1,3,5 -thiadiazin -4 -one (compound No. 377):

In a manner similar to that in Example 51, the reaction was carried out by using 2.4 g (0.006 mole) of I ,3,5-tris(2,4-dimethylphenyl)-hexahydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.1 g (0.016 mole of 1-methyl-3-iso- propylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution. After completion of the reaction, the n-hexane-insoluble matter was removed by filtration and the filtrate was freed from the n-hexane by distillation. The residue was dissolved in either and gaseous hydrogen chloride was passed through the ether solution. An ether insoluble oily substance immediately separated out and deposited on the bottom. After removal of the solvent, an excess amount of aqueous alkali solution was added to the oily substance and extracted with benzene. The benzene layer was washed with water, dehydrated, and concentrated to give 0.9 g (19% yield) of a colourless oily substance (n2D0 1.5674).

In a similar manner, 2.4 g (0.006 mole) of 1,3,5-tris(2,4-dimethylphenyl)-hexa- hydro-s-triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.5 g (0.0016 mole) of 1,3-diisopropylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.2 g (22% yield) of 2 - isopropylimino - 3 isopropyl - 5 - (2,4 - dimethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 378) of the formula,

as a light yellow oily substance (n2D 1.5589).

Similarly, 2.4 g (0.006 mole) of 1 ,3,5-tris(2,4-dimethylphenyl)-hexahydro-s- triazine, 1.8 g (0.009 mole) of trichloromethyl chloroformate, 2.9 g (0.016 mole) of l-isopropyl-3-t-butylthiourea, and 15 g of a 10% aqueous sodium hydroxide solution were used to obtain 1.0 g (18% yield) of 2 - t - butylimino - 3 - isopropyl 5 - (2,4 - dimethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 379):

as white crystals melting at 99--1000C.

In a similar manner, 3.3 g (0.007 mole) of 1,3,5-tris(2-methyl-4-chlorophenyl)- hexahydro-s-triazine, 2.0 g (0.01 mole) of trichloromethyl chloroformate, 3.2 g (0.018 mole) of l-isopropyl-3-t-butylthiourea, and 18 g of a 10% aqueous sodium hydroxide solution were used to obtain 0.5 g (7% yield) of 2 - t - butylimino - 3 isopropyl - 5 - (2 - methyl - 4 - chlorophenyl) - tetrahydro - 1,3,5 - thiadiazin 4 - one (compound No. 387) of the formula,

as white crystals melting at 122-1230C.

Similarly, 2.7 g (0.02 mole) of N-methylene-2,6-dimethylaniline, 2.0 g of trichloromethyl chloroformate, 2.0 g (0.02 mole) of 1,3-dimethylthiourea, and 18 g of alO% aqueous sodium hydroxide solution were used to obtain 0.6 g (12% yield) of 2 - methylimino - 3 - methyl - 5 - (2,6 - dimethylphenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 389) of the formula,

as a colourless oily substance (n30 1.5967).

Similarly, 2.7 g (0.02 mole) of N-methylene-2,6-dimethylaniline, 2.0 g (0.01 mole) of trichloromethyl chloroformate, 3.3 g (0.019 mole) of l-isopropyl-3-tbutylthiourea, and 18 g of a 10% aqueous sodium hydroxide solution were used to obtain 0.3 g (7% yield) of 2- t - butylimino - 3 - isopropyl - 5 - (2,6 dimethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 388) of the formula,

as white-crystals melting at 103--1040C.

Example 54.

2 - Isopropylimino - 3 - methyl - 5 - (2,6 - diethyiphenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one (compound No. 393):

A solution of 1.6 g (0.01 mole) of N-methylene-2,6-diethylaniline in 20 ml of benzene was added dropwise with stirring to 10 ml of a toluene solution containing 1.2 g of phosgene. After 10 minutes of stirring, 1.3 g (0.01 mole) of l-methyl-3- isopropylthiourea was added to the mixture and heated under reflux for one hour. The reaction mixture was admixed with 100 ml of water and the benzene layer was removed. The aqueous layer was made alkaline with 5 ml of a 30% potassium hydroxide solution and extracted with 100 ml of benzene. The benzene layer was washed with water, dried, and concentrated to obtain a viscous oily substance.

The oily substance was recrystallized from isopropyl alcohol to give 1.7 g (560 yield) of white crystals melting at 106--1070C.

Example 55.

2 - Isopropylimino-3-isopropyl - 5 - (2,6-diethylphenyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one (compound No. 395):

A solution of 1.6 g (0.01 mole) of N-methylene-2,6-diethylaniline in 10 ml of benzene was added with stirring to 10 ml of benzene containing 1.1 g of trichloromethyl chloroformate. After 10 minutes of stirring, a solution of 1.6 g (0.01 mole) of l,3-diisopropylthiourea in 20 ml of benzene was added to the mixture and heated under reflux with stirring for one hour. The reaction mixture was admixed with 100 ml of water and shaken thoroughly. The aqueous layer was separated and mixed with 5 ml of a 30% aqueous potassium hydroxide solution to deposit an oily substance which was extracted with benzene. l he benzene layer was washed with water, dried, and concentrated to a viscous oily substance which was recrystallized from isopropanol-n-hexane (8:2) to give 1.4 g (40% yield) of white crystals melting at 89-900C.

NMR(CDCI3) 8:3.50

Example 56.

2 - t - Butylimino - 3 - ethyl - 5 - phenyl - tetrahydro - 1,3,5 - thiadiazin 4 -one (compound No. 131):

A solution of 46 g of aniline in 250 ml of ethyl alcohol was mixed with 75 ml of 37% formalin and stirred for 30 minutes at room temperature. The precipitated crystals were collected by filtration, washed with ethyl alcohol and recrystallized from hot benzene to obtain l,3,5-triphenyl-hexahydro-s-triazine melting at 130-1330C. To a solution of .12 g of trichloromethyl chloroformate in 10 ml of benzene, was added dropwise with stirring a solution of 1.0 g (0.0033 mole) of the above 1,3,5-tri-phenyl-hexahydro-s-triazine in 20 ml of tetrahydrofuran, followed by a solution of 1.6 of l-ethyl-3-t-butylthiourea in 20 ml of benzene and then by 8 ml of a 15% aqueous potassium hydroxide solution. The reactant mixture was heated to 400 to 500 C. and stirred for 5 hours. The reaction mixture was poured into water and the separated benzene layer was washed with water and dried. The crude crystals obtained on removal of the benzene by distillation were recrystallized from isopropyl alcohol to give 1.0 g (38% yield) of white crystals melting at 93--940C.

In a similar manner, 1.0 g of 1,3,5-triphenyl-hexahydro-s-triazine, 1.1 g of trichloromethyl chloroformate, and 1.7 g of 1-isopropyl-3-t-butylthiourea were reacted to yield 1.2 g (40% yield) of 2 - t - butylimino - 3 - isopropyl - 5 phenyl - tetrahydro - 1,3,5 - thiadiazin - 4 - one (compound No. 145) of the formula,

in the form of white crystals melting at 106-1070C.

The under mentioned compounds of this invention are blended with auxiliary agents to give various compositions, according to the following formulations. The type and proportion of the compound and auxiliary agents, as well as the form of the composition, may be varied as required. The technique of blending and the technique of applying the composition are similar to those known to the art. In the following Examples all parts are by weight.

Example 57.

An emulsifiable concentrate was prepared by uniformly blending the following ingredients: Parts Compound No. 131 50 Xylene 40 Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 10 Example 58.

A dust composition was prepared by uniformly blending the following ingredients: Parts Compound No. 144 3 Powdered clay 82 Powdered diatomaceous earth 15 Example 59 A granule composition was prepared by uniformly blending the following ingredients, then kneading thoroughly with a suitable quantity of water, granulating, and drying.

Parts Compound No. 145 5 Mixture of powdered bentonite and clay 90 Calcium ligninsulfonate 5 Example 60 A wettable powder was prepared by uniformly mixing the following ingredients: Parts Compound No. 144 20 Mixture of powdered clay and synthetic high-dispersion silicic acid 75 Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 Example 61 An oil spray composition was prepared by mixing the following ingredients: Parts Compound No. 115 2 Kerosene 98 Example 62 A granule composition was prepared by dissolving the following ingredients in z suitable solvent and spraying over 95 parts of granular clay (10--48 mesh Tyler standard sieve in granule size) and drying.

Parts Compound No. 62 3 0,0-diethyl 0-(2-isopropyl-4-methylpyrimidyl-6) thiophosphate 2 Example 63 An emulsifiable concentrate was prepared by uniformly mixing the following ingredients: Parts Compound No. 18 50 Xylene 40 Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 10 Example 64 A dust composition was prepared by uniformly blending the following ingredients: Parts Compound No. 25 3 Powdered clay 82 Powdered diatomaceous earth 15 Example 65 A granule composition was prepared by uniformly mixing the following ingredients, kneading thoroughly with a suitable quantity of water, granulating, and drying.

Parts Compound No. 42 5 Mixture of powdered bentonite and powdered clay 90 Calcium ligninsulfonate 5 Example 66 A wettable powder was prepared by uniformly mixing the following ingredients: Parts Compound No. 48 20 Mixture of powdered kaolin and synthetic fine-dispersion silicic acid 75 Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 Example 67 An oil spray composition was prepared by mixing the following ingredients: Parts Compound No. 66 2 Kerosene 98 Example 68 A solution of 3 parts of the compound No. 87 in a suitable solvent was sprayed over 97 parts of granular clay (1048 mesh Tyler standard sieve in particles size) and dried to give a granule composition.

Example 69 An emulsifiable concentrate was prepared by uniformly mixing the following ingredients: Parts A compounds of this invention (No. 280) 50 Xylene 40 Polyoxyethylene nonphenyl ether admixed with calcium alkylbenzenesulfonate 10 Example 70 A dust composition was prepared by uniformly mixing the following ingredients: Parts Compound No. 318 3 Powdered clay 82 Powdered diatomaceous earth 15 Example 71 A granule composition was prepared by uniformly mixing the following ingredients, kneading sufficiently with a suitable quantity of water, granulating, and drying.

Parts Compound No. 195 5 Powdered mixture of bentonite and clay 90 Calcium ligninsulfonate 5 Example 72 A wettable powder was prepared by uniformly mixing the following ingredients: Parts Compound No. 241 20 Powdered mixture of kaoline and synthetic high-dispersion silicic acid 75 Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate 5 Example 73 An oil spray composition was prepared by mixing the following ingredients: Parts Compound No. 302 2 Kerosene 98 Example 74 A granule composition was prepared by dissolving the following ingredients in a suitable solvent and spraying over 95 parts of granular clay (10-48 mesh Tyler standard sieve in particle size) and drying.

Parts Compound No.316 3 0,0-diethyl 0-(2-isopropyl-4-methylpyrimidyl-6) thiophosphate 2 Test Example 1 Insecticidal activity against larvae of brown planthopper (Nilaparvata lugens Stall).

Testing method: Five rice seedlings of the 1.5 leaf age were dipped in a test composition of 400 ppm concentration for 30 seconds. After air-drying, the seedlings were placed in a glass tube containing I ml of water and infested with fve third-instar larvae of brown planthopper. The glass tube was left standing in a constant temperature cabinet at 250C and 5 to 7 days after the treatment, dead-and-survival was observed. Mortality was calculated from the results of 3-replication test.

The results obtained as shown in Table 1.

TABLE 1 *

Compound Mortality Compound Mortality Compound Mortality No. (%) No. (%) No. (%) 2 100 53 80 131 100 6 100 56 80 134 100 8 100 59 100 135 100 9 100 63 100 136 80 10 100 65 100 137 80 14 80 66 100 139 100 16 100 68 100 140 100 18 100 69 100 141 100 23 100 71 80 142 100 25 100 72 80 147 100 27 100 75 100 148 100 29 100 80 100 149 100 31 80 82 100 150 100 32 100 83 100 151 100 33 100 87 100 152 100 35 100 88 100 (155 50) 37 100 123 100 156 100 42 100 126 100 157 100 48 100 127 100 159 80 51 100 129 80 162 100 TABLE 1 * (cont.)

Compound Mortality Compound Mortality Compound Mortality No. (%) No. (%) No. (%) 167 70 241 100 293 100 179 90 242 100 294 100 182 70 243 100 295 100 188 100 244 100 297 100 194 100 245 100 299 100 196 100 247 90 300 100 197 100 248 100 301 100 198 ' 100 249 100 302 100 213 100 252 100 303 100 216 100 253 80 304 100 217 100 255 100 305 95 218 100 258 100 307 70 219 100 259 60 308 60 220 100 260 60 312 100 221 100 269 80 314 100 222 100 270 60 315 100 223 100 274 100 316 100 224 100 275 100 317 100 225 100 276 100 318 100 228 100 280 100 319 100 229 100 282 100 320 100 232 70 283 100 321 85 233 100 284 100 324 100 234 100 285 100 325 100 236 80 289 100 326 100 237 100 291 100 327 100 TABLE 1 * (cont.)

Compound Mortality Compound Mortality Compound mortality No. (%) No. (%) No. (%) 328 90 377 100 418 60 332 100 378 100 421 60 333 100 379 100 422 60 334 100 .380 100 425 60 335 80 381 60 426 70 336 100 382 80 427 100 337 100 | 383 100 428 100 338 100 384 100 339 100 385 100 342 100 387 100 343 100 388 100 344 100 390 60 Compound No. 2 No. 88: 350 100 394 70 | | | Data of 7 days 352 100 395 100 after treatment 353 100 398 100 Compound No. 126 354 100 399 100 No. 428: 355 100 400 100 Data of 5 days after treatment 360 100 401 100 364 100 402 80 367 80 406 80 368 80 407 100 371 75 409 60 372 60 411 60 373 80 412 100 374 80 415 100 376 60 416 100 Test Example 2 Insecticidal activity against larvae of white-backed planthopper (Sogatella furcifera Horv th).

Testing method: Five rice seedlings of the 1.5 leaf age were dipped in a test composition of 400 ppm concentration for 30 seconds. After air-drying, the seedlings were placed in a glass tube containing 1 ml of water and infested with five first-instar larvae of white-backed planthopper. The glass tube was .left standing in a constant temperature cabinet at 250C and seven days after the treatment, deadand-survival was observed. Mortality was calculated from the results of 3replication test.

The results obtained were as shown in Table 2.

TABLE 2

Compound Mortality Compound Mortality Compound Mortality No. (%) No. (g0) No. (6to) 2 100 66 100 283 100 6 100 68 100 284 100 8 100 69 100 285 100 9 100 71 80 291 100 10 100 72 100 302 100 14 100 75 100 303 100 16 100 80 100 316 100 18 100 82 100 318 100 23 100 83 100 319 100 25 100 87 100 325 100 27 100 88 100 326 100 29 100 144 100 327 100 31 100 145 100 328 100 32 100 151 100 333 100 33 100 152 100 352 100 35 100 196 90 353 100 37 100 197 90 355 100 42 100 198 100 395 90 48 100 220 100 51 100 221 100 53 80 224 100 56 80 225 100 59 100 244 100 63 100 245 100 65 100 0 282 100 Test Example 3 Activity to two-spotted spider mite (Tetranychus urticae Koch).

Testing method: Two-spotted spider mites were set free on the pot-planted soybean in a greenhouse. On the next day, a test composition of 1,000 ppm concentration was sprayed over the soybean by means of a spray gun. Two days or five days after the treatment, dead-and-survival was inspected to calculate the mortality.

The results obtained were as shown in Table 3.

TABLE 3 *

Compound Mortality Compound Mortality Compound Mortality No. (%) No. (%) No. (%) 2 100 59 100 218 100 6 100 63 80 219 70 8 100 65 100 221 100 9 80 66 100 222 80 10 100 68 100 1 223 70 14 100 69 100 224 100 16 100 71 100 225 100 18 80 72 100 233 100 23 100 75 80 237 100 25 100 80 80 241 70 27 80 82 100 242 70 29 100 83 100 244 70 31 100 87 100 245 100 32 100 88 100 247 70 33 100 188 90 248 100 35 100 194 100 249 70 37 100 196 100 255 100 42 100 197 80 258 | 100 48 100 198 100 259 100 51 100 213 100 260 100 53 100 216 70 270 70 56 100 217 100 274 100 * Compound No. 2 - No. 88: Data of 2 days after treatment Compound No. 188-No. 428: Data of 5 days after treatment TABLE 3 * (cont.)

Compound Mortality Compound Mortality Compound Mortality No. (%) No. (%) No. (%) 280 80 317 100 379 100 282 80 318 100 380 100 283 70 319 100 381 70 284 100 320 70 382 100 285 100 321 70 383 100 289 100 327 100 384 100 291 100 328 100 385 100 293 100 336 100 387 100 294 100 337 100 388 100 295 100 350 100 390 80 297 100 353 100 394 80 298 100 354 100 395 80 299 100 355 100 398 80 300 90 359 100 399 80 301 100 364 60 400 70 302 70 367 100 401 70 303 80 368 100 402 100 304 100 370 100 404 100 305 70 371 100 406 60 307 70 372 100 407 100 308 100 373 100 408 100 312 100 374 100 409 100 314 100 376 100 411 100 315 100 377 100 412 100 316 100 378 100 415 | 100 TABLE 3 * (cont.)

Compound Mortality Compound Mortality Compound Mortality No. (%) No. (%) No. (%) 416 100 421 70 426 100 418 70 422 100 427 100 419 100 425 100 428 100 lest Example 4 Activity to citrus red mite (Pannonychus citri McGregor).

Testing method: The test was performed by Rothamstead method. A test composition was sprayed by means of a spray gun over grapefruit leaves infested with citrus red mites. After air-drying, the grapefruit was left standing in a constant temperature cabinet at 250 C. Two days after the treatment, the number of survived mites was counted to calculate the mortality.

The results obtained were as shown in Table 4. TABLE 4

Compound Mortality Compound Mortality Compound Mortality No. (io) No. (No) No. (inc) 2 50 66 50 309 100 6 80 68 50 310 100 8 80 .69 80 316 100 9 50 71 50 319 100 10 80 72 80 368 100 14 50 75 50 16 100 80 100 18 100 82 100 23 80 83 50 25 80 87 100 27 100 88 100 29 100 115 100 31 100 118 100 32 100 123 100 33 100 124 100 35 100 131 100 37 100 135 100 42 100 145 100 48 100 148 100 51 50 153 100 53 100 161 100 56 100 218 100 59 100 219 100 63 50 249 100 65 100 281 100 Test Example 5 Activity against larvae of green rice leafhopper (Nephotettix cincticeps Uhler).

Testing method: Five rice seedlings of the 1.5 leaf age were dipped in a test composition of 400 ppm concentration for 30 seconds. After air-drying, the seedling were placed in a glass tube containing 1 ml of water and infested with five second-instar larvae of green rice leafhopper. The glass tube was left standing in a constant temperature cabinet at 250C. Seven days after the treatment, dead-andsurvival was inspected to calculate the mortality (3-replication test).

The results obtained were as shown in Table 5.

TABLE 5

Compound Mortality Compound Mortality Compound Mortality No. (%) No. ( iO) No. (%) 2 50 66 80 194 100 6 80 68 50 198 100 8 80 69 100 220 100 9 100 71 50 221 100 10 100 72 80 224 100 14 100 75 50 225 90 16 100 80 50 244 100 18 100 82 80 245 100 23 80 83 80 248 100 25 100 87 80 249 100 27 80 88 80 282 100 29 80 130 100 283 90 31 50 131 100 284 100 32 50 140 100 285 100 33 100 141 100 291 100 35 | 50 142 100 302 100 37 50 143 100 303 100 42 80 144 100 318 100 48 80 145 100 319 100 51 50 150 90 325 100 53 | 50 151 100 326 100 56 50 152 100 327 100 59 100 153 100 328 100 63 80 156 100 333 100 65 50 188 100 352 100 353 100 355 100 395 100 Test Example 6 Insecticidal activity to larvae of house mosquito (Culex pipiens pallens Coquillett).

Testing method: In a 200-ml beaker, was placed together with a feed 100 ml of a test composition diluted with deionized water to 10 ppm concentration. The test composition was infested with 20 first-instar larvae of house mosquito and the beaker was covered with a sheet of Japanese paper. The beaker was kept in a constant temperature cabinet at 25 C. Five days after the treatment, the dead-andsurvival was inspected to calculate the mortality.

The results obtained were as shown in Table 6.

TABLE 6

Compound Mortality Compound Mortality Compound Mortality No. (170) No. ('o) No.

125 80 157 100 | 282 90 126 100 162 100 283 70 127 100 188 100 284 100 129 100 194 80 285 100 131 100 197 100 291 70 134 80 198 100 301 90 135 100 213 100 302 100 136 100 218 100 | 307 100 137 100 220 80 308 100 139 100 221 100 310 100 140 100 223 100 312 100 141 100 224 100 314 100 142 100 225 100 315 100 143 80 244 100 316 70 144 100 245 100 317 100 145 100 247 100 318 -90 146 100 248 90 319 100 147 100 249 100 320 70 149 100 259 100 321 70 150 100 265 100 325 100 151 100 269 100 326 100 152 100 270 100 327 90 155 100 | 274 100 328 100 156 100 280 90 333 100 352 100 353 100 355 90 395 100 Test Example 7 Insecticidal activity to adult rust-red flour beetle (Tribolium castaneum Herbst).

Testing method: Into a 9-cm Petri dish covered on the bottom with a piece of filter paper, was introduced 7 ml of a test composition of 400 ppm concentration.

Ten adult rust-red flour beetles were released in the Petri dish and left standing in a constant temperature cabinet at 250C. After 24 hours, the dead-and-survival was inspected to calculate the mortality.

The results obtained were as shown in Table 7.

TABLE 7

Compound Mortality No. (%) 213 100 216 100 217 100 218 100 219 100 222 100 223 100 224 100 Test Example 8 Insecticidal activity against larvae of 28-spotted lady beetle (Epilachna vigintioctopunctana Fabricius).

Testing method: Leaflets of tomato grown in a greenhouse were dipped in a test composition of 100 ppm concentration for 30 seconds and after that the leaflets were dried by air. In a Petri dish covered on the bottom with a piece of filter paper, were introduced I ml of water and three treated tomato leaflets. After having been infested with seven second-instar larvae of 28-spotted lady beetle, the Petri dish was left standing in a constant temperature cabinet at 25"C. Five days after the treatment, the dead-and-survival was inspected to calculate the mortality (2replication test).

The results obtained were as shown in Table 8. TABLE 8

Compound Mortality Compound Mortality . Compound Mortality No. (%) No. (g) No. (neo) 126 80 155 100 325 100 127 80 156 90 326 100 131 100 157 100 327 100 134 ; 80 162 50 328 100 135 100 163 60 352 100 136 50 198 100 353 100 137 50 220 100 355 100 139 100 221 90 364 80 140 50 244 90 398 80 141 100 245 90 399 100 142 100 249 100 404 90 143 100 283 90 405 90 144 100 284 100 411 100 145 100 285 80 412 100 146 100 291 100 418 70 147 100 302 80 422 90 148 100 303 100 149 100 314 100 150 80 316 100 151 100 318 100 152 160 319 100 Test Example 9 Insecticidal activity against larvae of bug. (Togo hemipterus Scott).

Testing method: Into a glass tube 1.6 cm in internal diameter and 9 cm in length), was added I ml of a test composition in 10 ppm concentration just to moisten the absorbent cotton. Five rice seeds and five first-instar larvae were introduced into the glass tube and the tube end was covered with a piece of Japanese paper. The glass tube was kept in a constant temperature cabinet at 250 C.

Five days after treatment, the dead-and-survival was inspected to calculate the mortality (3-replication test).

The results obtained were as shown in Table 9.

TABLE 9

Compound Mortality Compound Mortality Compound Mortality No. (%) No. (%) No. (%) 118 100 139 100 151 80 126 100 140 50 152 100 127 100 141 80 155 100 129 100 142 100 156 50 131 100 143 100 157 100 134 80 144 100 162 50 135 100 145 100 216 100 1.36 100 149 50 217 100 137 50 150 50 222 100 Test Example 10 Insecticidal activity against larvae of diamond-back moth (Plutilla xylostella Linn'e).

Testing method: A test composition of 400 ppm concentration was sprayed over the pot-planted chinese cabbage in a greenhouse by means of a spray gun.

After air-drying, the chinese cabbage was infested with 10 first-instar larvae of diamond-back moth and was left standing in the greenhouse. Three days after the treatment, the dead-and-survival was inspected to calculate the mortality (3replication test).

The results obtained were as shown in Table 10.

TABLE 10

Compound Mortality Compound Mortality Compound Mortality mpound Mortality Compound Mortality Compound Mortal No. (%) No. (%) No. (%) 207 100 232 70 329

Claims (32)

1. WHAT WE CLAIM IS:- I. A tetrahydro-1,3,5-thiadiazin-4-one represented by the general formula,

   (wherein R', R2 and R3, which may be the same or different, each represent an alkyl group of C1 to 8. allyl group, cycloalkyl group of C3 to Ca, alkoxyalkyl group having a total of 3 to 6 carbon atoms, benzyl group, phenyl group or substituted phenyl group having one or two substitiuents selected from alkyl groups of C, to C4, nitro groups, halogen atoms, alkoxy groups of C1 to C4 and trifluoromethyl groups, R' may also represent a p-hydroxyphenyl group, R2 may also represent a hydrogen atom of a furfuryl group, and R3 may also represent a hydrogen atom) or an acid addition salt thereof.
2. 2. A tetrahydro-I,3,5-thiadiazin-4-one or an acid addition salt thereof according to Claim I, wherein R2 and R3, which may be the same or different, are alkyl groups of C, to Ca.
3. 3. A tetrahydro-l,3,5-thiadiazin-4-one or an acid addition salt thereof according to Claim I or 2, wherein R' is a phenyl group.
4. 4. A tetrahydro-l ,3,5-thiadiazin-4-one or an acid addition salt thereof according to Claim I or 2, wherein R' is a substituted phenyl group having one or two substituents selected from alkyl groups of C, to C4, nitro groups, halogen atoms, and alkoxy groups of C, to C4.
5. 5. 2 - t - Butylimino - 3 - isopropyl - 5 - phenyl - tetrahydro - 1,3,5 thiadiazin - 4 - one or an acid addition salt thereof.
6. 6. 2 - t - Butylimino - 3 - isopropyl - 5 - (4 - tolyl) - tetrahydro - 1,3,5thiadiazin - 4 - one or an acid addition salt thereof.
7. 7. 2 - t - Butylimino - 3 - isopropyl - (3 - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one or an acid addition salt thereof.
8. 8. 2 - t - Butylimino - 3 - isopropyl - (3 - tolyl) - tetrahydro - 1,3,5 thiadiazin - 4 - one or an acid addition salt thereof.
9. 9. 2 - t - Butylimino - 3 - sec - butyl - 5 - (2,4 - dimethylphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one or an acid addition salt thereof
10. 10. 2 - t - Butylimino - 3 - isopropyl - 5 - (2 - chlorophenyl) - tetrahydro 1,3,5 - thiadiazin - 4 - one or acid addition salt thereof,
11. Il. 2 - t - Butylimino - 3 - isopropyl - 5 - (4 - methoxyphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one or an acid addition salt thereof.
12. 12. 2 - t - Butylimino -3-sec - butyl - 5 - (4 - methoxyphenyl) - tetrahydro - 1,3,5 - thiadiazin - 4 - one or an acid addition salt thereof.
13. 13. An acid addition salt of a tetrahydro-1,3,5-thiadiazin-4-one according to any of Claims 1 to 12, wherein the acid is an inorganic acid.
14. 14. A method for producing a tetrahydro-1,3,5-thiadiazin-4-one as claimed in claim 1, or an acid addition salt thereof, which comprises reacting a carbamoyl chloride represented by the general formula,

    wherein R1 is as defined in claim 1, with a thiourea represented by the general formula,

    wherein R2 and R3 are as defined in claim 1.
15. 15. A method according to Claim 14, wherein the reaction is carried out in the presence of a base.
16. 16. A method according to Claim 14, wherein the reaction is carried out in the absence of a base to yield a tetrahydro-1,3,5-thiadiazin-4-one in the form of a hydrochloride.
17. 17. A method according to any of Claims 14 to 16, wherein R2 and R3, which may be the same or different, in the general formulas (I) and (III), each represent an alkyl group of C, to Ca.
18. 18. A method according to any of Claims 14 to 17, wherein R' in the general formulas (I) and (II) represents a phenyl group.
19. 19. A method according to any of Claims 14 to 17, wherein R1 in the general formula (I) represents a substituted phenyl group having one or two substituents selected from alkyl groups of C, to C4, nitro groups, halogen atoms, and alkoxy groups of C, to C4.
20. 20. An insecticidal and miticidal composition comprising a tetrahydro-1,3,5thiadiazin-4-one as claimed in claim 1, or an acid addition salt thereof, and an inert diluent.
21. 21. A composition according to Claim 20 for use in controlling insects and mites injurious to agricultural crops.
22. 22. A composition according to any of Claims 20 and 21 for use in controlling planthoppers and leafhoppers.
23. 23. A composition according to any of Claims 20 to 22, wherein R2 and R3 in the general formula (I), which may the same or different, each represent an alkyl group of C, to Ca.
24. 24. A composition according to any of Claims 20 to 23, wherein R' in the general formula (I) represents a phenyl group.
25. 25. A composition according to any of Claims 20 to 23, wherein R' in the general formula (I) represents a substituted phenyl group having one or two substituents selected from alkyl groups of C, to C4, nitro group, halogen atoms, and alkoxy groups of C, to C4.
26. 26. A composition according to Claim 20, wherein the composition contains 2t-butylimino-3-isopropyl-5-phenyl-tetrahydro- 1,3 ,5-thiadiazin-4-one or an acid addition salt thereof.
27. 27. A composition according to Claim 20, wherein the composition contains 2 t-butylimino-3-isopropyl-5-(p-tolyl)-tetrahydro- 1 ,3,5-thiadi azin-4-one or an acid addition salt thereof.
28. 28. A method for protecting agricultural crops from injurious insects and mites, which comprises applying to the agricultural crops or the soil where the agricultural crops are grown an effective amount of a tetrahydro-l ,3,5-thiadiazin-4one as claimed in claim 1, or an acid addition salt thereof.
29. 29. A compound as claimed in claim 1, being any of the compounds Nos.

    1--144, 146-220, 222-244, 246-317, 319-325, 327-352, 354, 356-379 and 381433 hereinbefore listed, or an acid addition salt thereof.
30. 30. A method as claimed in claim 14, substantially as described in any of Examples 1--56 herein.
31. 31. A composition according to claim 20, substantially as described in any of Examples 57-74 herein.
32. 32. A compound as claimed in claim 1, produced by a method as claimed in any of claims 14 to 19, or claim 30.