CN1204328A - 1,3-oxazin-4-one derivatives as herbicides - Google Patents

Abstract

1,3-Oxazin-4-one derivatives of formula (I): wherein Q represents -C(=O)-, -CH(OH)- or -C(OR11)(OR11)-, in which R11 represents lower alkyl; or the two groups -OR11, together with the carbon atom to which they are attached, form a five or six membered cyclic ketal group; and their use as herbicides.

Description

As 1 of weedicide, 3-oxazine-4-ketone derivatives

The present invention relates to newly 1,3-oxazine-4-ketone derivatives, contain the herbicidal composition of this derivative and be used to make the new intermediate of this derivative.

International publication WO93/15064 disclose certain 1,3-oxazine-4-ketone derivatives (as 2,3-dihydro-6-methyl-3-(1-methyl isophthalic acid-phenylethyl)-5-phenyl-4H-1,3-oxazine-4-ketone) and weeding activity thereof.But the described compound of described publication does not have ketone or carbinol-functional degree with 1 on the group that the 3-position nitrogen-atoms of 3-oxazine ring links to each other.

The invention provides 1 of a kind of formula I, 3-oxazine-4-ketone derivatives and have acceptable salt on the agricultural of useful performance:

Wherein, R ¹The phenyl that expression can be replaced arbitrarily by 1-5 group, described group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁷,-CO ₂R ⁷,-COR ⁷, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁷And phenoxy group;

5-7 unit hetero-aromatic ring with 1-4 heterocyclic atom, described heterocyclic atom can be identical or different, be selected from nitrogen, oxygen and sulphur, described heterocycle at random by 1-4 identical or different be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁷,-CO ₂R ⁷,-COR ⁷, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁷Replace with the group of phenoxy group;

Or contain 10 carbon atoms and at random halogenated straight or branched alkyl, alkenyl or alkynyl at most;

R ²Representative:

Hydrogen atom; Or

Have 1-10 carbon atom, at random by one or more identical or different R ⁸The straight or branched alkyl that group replaced;

Be up to 10 carbon atoms also at random by halogenated straight or branched alkenyl or alkynyl;

Or be selected from cyano group ,-CHO ,-COR ⁷,-CO ₂H ,-CO ₂R ⁷-,-COSR ⁷,-CONR ⁹R ¹⁰,-CH=NOH ,-CH=NOR ⁷,-CH=NOCOR ⁷,-CH=NNR ⁹R ¹⁰,-CH ₂CN ,-CH ₂NO ₂Group with Oxyranyle;

R ³Representative-(CH ₂) _r-(phenyl or naphthyl that is replaced by 1-5 group at random, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶, phenoxy group and-SF ₅);

-(CH ₂) _s-(5-7 unit hetero-aromatic ring with 1-4 heterocyclic atom, described heterocyclic atom can be identical or different, be selected from nitrogen, oxygen and sulphur, described heterocycle can at random condense with phenyl ring, perhaps condense with second 5-7 unit hetero-aromatic ring with 1-4 identical or different heterocyclic atom that is selected from nitrogen, oxygen and sulphur, form two member ring systems, any one ring in monocycle or two member ring systems can at random be replaced by 1-4 group, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶And phenoxy group);

Be up to 10 carbon atoms and can at random halogenated straight or branched alkyl, alkenyl or alkynyl;

Be up to 10 carbon atoms, halogenation at random and straight or branched alkyl, alkenyl or alkynyl with cycloalkyl substituted of 3-6 carbon atom; Perhaps

Have the cycloalkyl of 3-6 carbon atom or have the cycloalkenyl group of 5-6 carbon atom, their ring can be at random by identical or different R ⁶Group or one or more halogen atom replace;

R ⁴And R ⁵Represent low alkyl group respectively;

R ⁶And R ⁷Represent low alkyl group or low-grade halogenated alkyl respectively;

N represents 0,1 or 2;

Q represents 1 or 2;

R represents 0,1 or 2; S represents 0 or 1;

R ⁸Be halogen ,-OH ,-OR ⁷,-OCOR ⁷,-S (O) _nR ⁷,-NR ⁹R ¹⁰Or trinitride;

R ⁹And R ¹⁰Represent hydrogen, low alkyl group or low-grade halogenated alkyl respectively;

Q representative-C (=O)-,-CH (OH)-or-C (OR ¹¹) (OR ¹¹)-; R wherein ¹¹Represent low alkyl group; Perhaps two-OR ¹¹Group forms 5 yuan or 6 yuan of ring ketal groups with the carbon atom that they connected.

Term " acceptable salt on the agricultural " refers to salt, and its positively charged ion or negatively charged ion are known in agricultural or gardening in the manufacturing field with salt and are acceptable.Salt is water miscible preferably.Suitable salt has alkalescence, comprises the salt of basic metal (as sodium and potassium), salt, ammonium and amine (as diethanolamine, trolamine, octylame, morpholine and the dioctyl methylamine) salt of alkaline-earth metal (as calcium and magnesium).Suitable acid salt (as the salt that is made by the amino formula I compound of band) comprises salt that forms with mineral acid (example hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid) and the salt that forms with organic acid (as acetate).

R in some cases ¹-R ¹¹Group can produce steric isomer and geometrical isomer.The present invention includes all these isomer.

Except as otherwise noted, otherwise generally following term is defined as:

" low alkyl group " refers to have the straight or branched alkyl of 1-6 carbon atom;

" low-grade halogenated alkyl " refers to the straight or branched alkyl that has 1-6 carbon atom and replaced by one or more halogens;

" lower alkoxy " refers to have the straight or branched alkoxyl group of 1-6 carbon atom;

" elementary halogenated alkoxy " refers to the straight or branched alkoxyl group that has 1-6 carbon atom and replaced by one or more halogens;

" halogen " refers to fluorine, chlorine, bromine or iodine atom.

In the following description, several classes (because its herbicidal performance) above-mentioned formula I compound preferably will be disclosed.

Preferably in the formula I compound, R ³Be-(CH ₂) _r-(phenyl that is replaced by 1-5 group at random, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶And phenoxy group);

-(CH ₂) _s-(5-7 unit hetero-aromatic ring with 1-4 heterocyclic atom, described heterocyclic atom can be identical or different, be selected from nitrogen, oxygen and sulphur, described heterocycle can at random condense with phenyl ring, perhaps condense with second 5-7 unit hetero-aromatic ring with 1-4 identical or different heterocyclic atom that is selected from nitrogen, oxygen and sulphur, form two member ring systems, any one ring in monocycle or two member ring systems can at random be replaced by 1-4 group, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶And phenoxy group); Or

Be up to 10 carbon atoms and can at random halogenated straight or branched alkyl, alkenyl or alkynyl; Or

Cycloalkyl with 3-6 carbon atom, it can be at random by identical or different R ⁶Group or one or more halogen atom replace;

R is 0 or 1; R ⁸It or not trinitride.

R ¹Representative at random is selected from the phenyl that group replaced of halogen, low alkyl group and low-grade halogenated alkyl or the above-mentioned formula I compound of thienyl is preferably by one or more.R ¹Phenyl preferably.

The above-mentioned formula I of class compound also comprises R wherein preferably ²Representative has the straight or branched alkyl of 1-6 carbon atom, the preferably compound of methyl.

That best is R ⁴And R ⁵The above-mentioned formula I compound of difference represent methylidene.

Q representative-C (=O)-above-mentioned formula I compound because its weeding activity but best.Q is-CH (OH)-above-mentioned formula I compound weeding activity generally than Q be-C (=O)-the weeding activity of respective compound of formula I low, it also can be used as the intermediate for preparing the latter.

R ³The above-mentioned formula I compound that is cyclopentyl is preferably, because it has high weeding activity for the weeds in the rice.

R ³The above-mentioned formula I compound that is normal-butyl or butenyl (as the 3-butenyl) also is preferably, because it is for unmanageable cereal weeds, (Alopecurus Myosuroides) has herbicidal effect as mouse tail amur foxtail.

Best above-mentioned formula I compound be those wherein:

R ¹The phenyl that representative is at random replaced by halogen;

R ², R ⁴And R ⁵The difference represent methylidene;

Q representative-C (=O)-; And

R ³Representative-(CH ₂) _r-(phenyl that at random is selected from halogen and has 1 or 2 carbon atoms and can at random be replaced) by the group of halogenated alkyl by 1 or 2 or;

Be up to straight or branched alkyl, the alkenyl or alkynyl of 4 carbon atoms;

R is 0 or 1 compound.

Preferred above-mentioned formula I compound be those wherein:

R ¹Representative is at random by halogen or methyl substituted phenyl or thienyl;

R ², R ⁴And R ⁵The difference represent methylidene;

Q representative-C (=O)-;

R ³Representative-(CH ₂) _r-(phenyl that at random is selected from halogen or has 1 or 2 carbon atoms and can at random be replaced) by the group of halogenated alkyl by 1 or 2;

Be up to the straight or branched alkyl or alkenyl of 6 carbon atoms;

Or has a cycloalkyl of 3-6 carbon atom;

R is 0 or 1 compound.

Another kind of best above-mentioned formula I compound is those compounds with one or more following features:

R ¹Representative is at random by the phenyl or the thienyl of halogen or methoxyl group replacement;

R ², R ⁴And R ⁵The difference represent methylidene;

Q representative-C (=O)-;

R ³Representative-(CH ₂) _r-(at random being selected from the phenyl that group replaced of halogen or methyl) by one or two;

At random by thienyl, furyl, benzothiazolyl or pyridyl that halogen or any halogenated methyl replaced;

Be up to 8 carbon atoms and can at random halogenated straight or branched alkyl, alkenyl or alkynyl; Perhaps

Cycloalkyl with 3-6 carbon atom; And

R is 0 or 1.

R ⁴And R ⁵Be methyl and Q be-C (=O)-following above-mentioned formula I compound constituted a part of the present invention.In following table, " Ph " refers to that phenyl, " Me " nail base, " Et " refer to that ethyl, " Pr " refer to that propyl group, " Bu " refer to butyl.Omitted subscript behind atom, CH=CH2 is meant-CH=CH but for example should understand ₂Or the like.

Compound number	R 1	R 2	R 3
				????1	????Ph	????Me	????i-Pr
????2	????Ph	????Me	????n-Bu
				????3	????Ph	????Me	3，5-F2?Ph
????4	????Ph	????Me	The 2-F-5-CF3 phenyl
				????5	????Ph	????Me	The 3-Cl benzyl
????6	????Ph	????Me	The 3-CF3 benzyl
				????7	????Ph	????Me	????CH2CH=CH2
????8	????Ph	????Me	????CH=CH2
				????9	The 2-F phenyl	????Me	The 4-F phenyl
????10	????Ph	????Me	Ethynyl
				????11	The 2-F phenyl	????Me	The 2-Me phenyl
????12	The 2-F phenyl	????Me	The 4-F-3-Me phenyl
				????13	????Ph	????Me	The 2-Me phenyl
????14	????Ph	????Me	The 4-F phenyl
				????15	????Ph	????Me	The 4-F-3-Me phenyl
????16	????Ph	????Me	Phenyl
				????17	????Ph	????Me	The 2-Cl phenyl
????18	????Ph	????Me	The 3-Cl phenyl
				????19	????Ph	????Me	The 4-Cl phenyl
????20	????Ph	????Me	The 3-CF3 phenyl
				????21	????Ph	????Me	3, the 5-Cl2 phenyl

????22	????Ph	????Me	2, the 5-F2 phenyl
				????23	????Ph	????Me	The 2-pyridyl
????24	????Ph	????Me	The 4-pyridyl
				????25	????Ph	????Me	4-methylthiazol-2-base
????26	????Ph	????Me	5-chlorine thiazol-2-yl
				????27	????Ph	????Me	????Me
????28	????Ph	????Me	????Et
				????29	????Ph	????Me	????n-Pr
????30	????Ph	????Me	????i-Bu
				????31	????Ph	????Me	Cyclopropyl
????32	????Ph	????Me	Sec-butyl
				????33	????Ph	????Me	Cyclobutyl
????34	????Ph	????Me	N-pentyl
				????35	????Ph	????Me	N-hexyl
????36	????Ph	????Me	Cyclohexyl
				????37	????Ph	????Me	N-heptyl
????38	????Ph	????Me	N-octyl
				????39	????Ph	????Me	3, the 5-Cl2 benzyl
????40	The 2-F phenyl	????Me	3, the 5-Cl2 phenyl
				????41	The 2-F phenyl	????Me	The 3-CF3 phenyl
????42	The 2-F phenyl	????Me	4-methylthiazol-2-base
				????43	The 2-F phenyl	????Me	Normal-butyl
????44	The 2-F phenyl	????Me	Cyclobutyl
				????45	The 2-F phenyl	????Me	The 3-Cl benzyl
????46	The 2-OMe phenyl	????Me	3, the 5-Cl2 phenyl
				????47	The 2-OMe phenyl	????Me	The 3-CF3 phenyl
????48	The 2-OMe phenyl	????Me	Normal-butyl
				????49	The 2-OMe phenyl	????Me	N-propyl
????50	The 2-OMe phenyl	????Me	The 2-pyridyl
				????51	The 3-Cl phenyl	????Me	Normal-butyl
????52	The 3-Cl phenyl	????Me	3, the 5-Cl2 phenyl

????53	The 2-thienyl	????Me	3, the 5-Cl2 phenyl
				????54	The 2-thienyl	????Me	The 3-CF3 phenyl
????55	The 2-thienyl	????Me	4-methylthiazol-2-base
				????56	The 2-thienyl	????Me	Normal-butyl
????57	The 2-thienyl	????Me	Cyclobutyl
				????58	The 2-thienyl	????Me	The 3-Cl benzyl
????59	The 2-furyl	????Me	3, the 5-Cl2 phenyl
				????60	Isobutyl-	????Me	3, the 5-Cl2 phenyl
????61	Isobutyl-	????Me	Normal-butyl
				????62	Isobutyl-	????Me	The 3-Cl benzyl
????63	4-methyl-1-pentene alkynyl	????Me	The 3-CF3 phenyl
				????64	4-methyl-1-pentene alkynyl	????Me	Normal-butyl
????65	4-methyl-1-pentene alkynyl	????Me	The 4-pyridyl
				????66	4-methyl-1-pentene alkynyl	????Me	Ethyl
????67	4-methyl-1-pentene alkynyl	????Me	3, the 5-Cl2 phenyl
				????68	4-methyl-1-pentene alkynyl	????Me	Normal-butyl
????69	????Ph	????CH2F	3, the 5-Cl2 phenyl
				????70	????Ph	????CH2F	Normal-butyl
????71	????Ph	????CH2F	The 3-Cl benzyl
				????72	????Ph	????CH2F	5-chlorine thiazol-2-yl
????73	????Ph	??CH2OMe	The 3-CF3 phenyl
				????74	????Ph	??CH2OMe	Isobutyl-
????75	????Ph	??CH2OMe	3, the 5-Cl2 benzyl
				????76	????Ph	??CH2OMe	Cyclohexyl
????77	????Ph	??CH2SMe	3, the 5-Cl2 phenyl
				????78	????Ph	??CH2SMe	Normal-butyl
????79	????Ph	??CH2SMe	The 3-Cl benzyl
				????80	????Ph	??CH2SMe	5-chlorine thiazol-2-yl
????81	????Ph	????CHF2	The 3-CF3 phenyl
				????82	????Ph	????CHF2	Isobutyl-
????83	????Ph	????CHF2	3, the 5-Cl2 benzyl

????84	????Ph	????CHF2	Cyclohexyl
				????85	????Ph	??CH=NOMe	3, the 5-Cl2 phenyl
????86	????Ph	??CH=NOMe	Normal-butyl
				????87	The 2-F phenyl	??CH2SMe	3, the 5-Cl2 phenyl
????88	The 2-F phenyl	??CH2OMe	Normal-butyl
				????89	The 2-thienyl	????CH2F	3, the 5-Cl2 phenyl
????90	????Ph	????Me	The tertiary butyl
				????91	????Ph	????Me	The 2-thienyl
????92	????Ph	????Me	The 2-furyl
				????93	????Ph	????Me	The 2-[4-morpholinodithio base
????94	????Ph	????Me	3, the 4-Cl2-benzyl
				????95	????Ph	????Me	3, the 5-Me2-benzyl
????96	????Ph	????Me	The 4-Cl-benzyl
				????97	????Ph	????Me	Cyclopentyl
????98	????Ph	????Me	The 3-Me-benzyl
				????99	????Ph	????Me	Benzyl
????100	????Ph	????Me	3, the 5-F2-benzyl
				????101	????Ph	????Me	The 6-Me-2-pyridyl
????102	????Ph	????Me	????-(CH2)2CH(Me)2
				????103	????Ph	????Me	The 4-CF3-2-pyridyl
????104	????Ph	????Me	2, the 5-F2-benzyl
				????105	????Ph	????Me	The 2-Cl-benzyl
????106	????Ph	????Me	2, the 4-F2-benzyl
				????107	????Ph	????Me	The 4-F-benzyl
????108	????Ph	????Me	????-(CH2)2CH=CH2
				????109	????Ph	????Me	????-CH(Me)CH2CH2Me
????110	????2-F?Ph	????Me	????-CH2CH=CHMe
				????111	????2-F?Ph	????Me	????n-Pr
????112	????2-OMe?Ph	????Me	????n-Pr
				????113	????2-OMe?Ph	????Me	????-(CH2)2CH=CH2
????114	????Ph	????Me	Cyclohexyl

????115	????Ph	????Me	????-CH2CH(Me)CH2Me
				????116	????Ph	????Me	????-(CH2)2CMe3
????117	????Ph	????Me	????-CH(CH2Me)2
				????118	????Ph	????Me	????-CH2CMe3
????119	The 2-thienyl	????Me	????-(CH2)2CH=CH2
				????120	The 2-thienyl	????Me	Cyclopentyl
????121	????Ph	????Me	????-(CH2)3CF3
				????122	????Ph	????Me	The 3-butynyl
????123	????Ph	????Me	??-(CH2)2CH(Me)CH2Me
				????124	????2-F?Ph	????Me	Cyclopentyl
????125	????2-Cl?Ph	????Me	Cyclopentyl
				????126	????2-Me?Ph	????Me	Cyclopentyl
????127	????2-Br?Ph	????Me	Cyclopentyl
				????128	????4-F?Ph	????Me	Cyclopentyl
????129	????2-F?Ph	????Me	The 3-butynyl
				????130	????2-Cl?Ph	????Me	The 3-butynyl
????131	????2-Me?Ph	????Me	The 3-butynyl
				????132	????2-Br?Ph	????Me	The 3-butynyl
????133	????4-F?Ph	????Me	The 3-butynyl
				????134	The 2-thienyl	????Me	The 3-butynyl
????135	????2-Cl?Ph	????Me	Normal-butyl
				????136	????2-Me?Ph	????Me	Normal-butyl
????137	????2-Br?Ph	????Me	Normal-butyl
				????138	????4-F?Ph	????Me	Normal-butyl
????139	????Ph	????Me	The 1-cyclopentenyl
				????140	????Ph	????Me	The 2-cyclopentenyl
????141	????Ph	????Me	The cyclopropyl methyl
				????142	????Ph	????Me	Cyclobutylmethyl
????143	????Ph	????Me	Cyclopentyl-methyl
				????144	????Ph	????Me	???-(CH2)2(3-Cl?Ph)
????145	????Ph	????Me	??-(CH2)2(4-OMe?Ph)

????146	????Ph	????Me	??-(CH2)2(3,5-Cl2?Ph)
				????147	????Ph	????Me	??-(CH2)2(3,5-F2?Ph)
????148	????Ph	????Me	????-(CH2)2(4-F?Ph)
				????149	????Ph	????Me	????-(CH2)2(2-Me?Ph)
????150	????Ph	????Me	??-(CH2)2(3-CF3?Ph)
				????151	????Ph	????Me	??-(CH2)2(2,5-F2?Ph)
????152	????2-F?Ph	????Me	????-(CH2)2CH=CH2
				????153	????2-Me?Ph	????Me	????-(CH2)2CH=CH2
????154	????2-Br?Ph	????Me	????-(CH2)2CH=CH2
				????155	????2-C1?Ph	????Me	????-(CH2)2CH=CH2
????156	????Ph	????CH2F	????-(CH2)2CH=CH2
				????157	????Ph	??CH2OMe	????-(CH2)2CH=CH2
????158	????Ph	??CH2SMe	????-(CH2)2CH=CH2
				????159	????Ph	???CH2N3	????-(CH2)2CH=CH2
????160	????Ph	????Me	The CH2-cyclopropyl
				????161	????Ph	????Me	The CH2-cyclobutyl
????162	????Ph	????Me	The CH2-cyclopentyl
				????163	????Ph	????Me	????(CH2)2(4-Cl?Ph)
????164	????Ph	????Me	??-CH2C(Me)2CH=CH2
				????165	????Ph	????Me	??-CH2C(Me)2CH=CH2
????166	????2-F?Ph	????Me	The CH2-cyclopropyl
				????167	????2-F?Ph	????Me	The CH2-cyclobutyl
????168	????2-F?Ph	????Me	The CH2-cyclopentyl
				????169	????2-F?Ph	????Me	????(CH2)2(4-Cl?Ph)
????170	????2-F?Ph	????Me	??-CH2C(Me)2CH=CH2
				????171	????2-F?Ph	????Me	??-CH2C(Me)2CH=CH2
????1?72	The 2-thienyl	????Me	The CH2-cyclopropyl
				????173	The 2-thienyl	????Me	The CH2-cyclobutyl
????174	The 2-thienyl	????Me	The CH2-cyclopentyl
				????175	The 2-thienyl	????Me	????(CH2)2(4-Cl?Ph)
????176	The 2-thienyl	????Me	??-CH2C(Me)2CH=CH2

????177	The 2-thienyl	????Me	??-CH2C(Me)2CH=CH2
				????178	????Ph	??CH2OMe	The CH2-cyclopropyl
????179	????Ph	??CH2F	The CH2-cyclopentyl
				????180	????Ph	??CH2F	Cyclopentyl
????181	????Ph	??CH2OMe	Cyclopentyl
				????182	????Ph	??CH2OEt	Cyclopentyl
????183	????Ph	??CH2SMe	Cyclopentyl
				????184	????Ph	??CHF2	Cyclopentyl
????185	????Ph	??CH=NOMe	Cyclopentyl
				????186	????Ph	??CH2N3	Cyclopentyl
????187	????2-F?Ph	??CH2F	Cyclopentyl
				????188	????2-F?Ph	??CH2OMe	Cyclopentyl
????189	????2-F?Ph	??CH2OEt	Cyclopentyl
				????190	????2-F?Ph	??CH2SMe	Cyclopentyl
????191	????2-F?Ph	??CHF2	Cyclopentyl
				????192	????2-F?Ph	??CH=NOMe	Cyclopentyl
????193	????2-F?Ph	??CH2N3	Cyclopentyl
				????194	The 2-thienyl	??CH2F	Cyclopentyl
????195	The 2-thienyl	??CH2OMe	Cyclopentyl
				????196	The 2-thienyl	??CH2OEt	Cyclopentyl
????197	The 2-thienyl	??CH2SMe	Cyclopentyl
				????198	The 2-thienyl	??CHF2	Cyclopentyl
????199	The 2-thienyl	??CH=NOMe	Cyclopentyl
				????200	The 2-thienyl	??CH2N3	Cyclopentyl
????201	????Ph	??Me	????3-OMe-5-Cl?Ph
				????202	????2-F?Ph	??Me	????3-OMe-5-Cl?Ph
????203	The 2-thienyl	??Me	????3-OMe-5-Cl?Ph
				????204	????2-Me?Ph	??Me	????3-OMe-5-Cl?Ph
????205	????2-Br?Ph	??Me	????3-OMe-5-Cl?Ph
				????206	????2-Cl?Ph	??Me	????3-OMe-5-Cl?Ph
????207	????4-F?Ph	??Me	????3-OMe-5-Cl?Ph

The evaluation that these compound number 1-207 is for reference and later is used:

Following formula I compound is preferably:

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-methyl-propione;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-heptanone;

1-(3, the 5-difluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(2-fluoro-5-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(3-trifluoromethyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-5-hexene-3-one;

4-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene-3-ketone;

1-(4-fluorophenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone;

4-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene alkynes-3-ketone;

2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-1-(2-aminomethyl phenyl)-2-methyl isophthalic acid-acetone;

1-(4-fluoro-3-aminomethyl phenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(2-aminomethyl phenyl)-1-acetone;

1-(4-fluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(4-fluoro-3-aminomethyl phenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-phenyl-1-acetone;

1-(2-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(4-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3, the 5-dichlorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-hexanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5-dimethyl-3-hexanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-propione;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-hendecanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-3-hexanone;

1-cyclopropyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4,4-trimethylammonium-propione;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(2-thienyl)-1-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-1-(3-furyl)-2-methyl isophthalic acid-acetone;

1-(2-[4-morpholinodithio base (benzthiazolyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-Evil piperazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3, the 4-dichlorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(3, the 5-dichlorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-1-(3, the 5-3,5-dimethylphenyl)-3-methyl-2-butanone;

1-(4-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-cyclopentyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl isophthalic acid-(3-aminomethyl phenyl)-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-nonanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-octanone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl isophthalic acid-(phenyl)-2-butanone;

1-(3, the 5-difluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(6-picoline-2-yl)-1-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6-dimethyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(4-5-flumethiazine-2-yl)-1-acetone;

1-(2, the 5-difluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(2-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(2,4 difluorobenzene base)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(4-fluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-6-teracrylic acid-ketone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-3-heptanone;

2-[2,3-dihydro-5-(2-fluorophenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-5-teracrylic acid-ketone;

2-[2,3-dihydro-5-(2-fluorophenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone;

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone;

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone;

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-6-teracrylic acid-ketone;

1-cyclohexyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone;

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5-dimethyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6,6-trimethylammonium-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-ethyl-2-methyl-3-hexanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5,5-trimethylammonium-3-hexanone;

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-6-teracrylic acid-ketone;

1-cyclopentyl-2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone;

1-cyclobutyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-7,7,7-three fluoro-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6-dimethyl-3-octanone; And

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-6-heptyne-3-ketone.

Can use or adopt known method (method of describing in the used or document before promptly) to prepare the compound of above-mentioned formula I.Should understand in the description of following method, its order can change, and needs the compound of suitable blocking group to obtain to require.

According to characteristics of the present invention, the formula I respective compound of oxidable Q representative-CH (OH)-group, make Q representative-C (=O)-the formula I compound of group.The suitable oxygenant (as chromic acid or pyridinium chlorochromate) of general use carries out this oxidation.This reaction can be carried out to the temperature of the reflux temperature of this solvent in suitable solvent (as ether or methylene dichloride) and at 0 ℃.

According to another characteristics of the present invention, can pass through formula II (R ¹, R ², R ⁴And R ⁵Aldehyde as defined above) and formula R ³-M (R ³As defined above, M represents metal group, is preferably magnesium bromide group or lithium atom) organometallic compound reaction and make Q representative-CH (OH)-the formula I compound:

This reaction is normally carried out to the temperature of the reflux temperature of this solvent at-78 ℃ in inert solvent (as ether or tetrahydrofuran (THF)).

According to another characteristics of the present invention, can make Q representative-C (=O)-formula I compound and formula R ¹¹The alcohol reaction of-OH makes Q representative-C (OR ¹¹) (OR ¹¹)-the formula I compound.This reaction generally is to carry out to the temperature of the reflux temperature of this solvent at 60 ℃ in the presence of acid catalyst (as the 4-toluenesulphonic acids) and inert solvent (as toluene).Can promote reaction by the water (preferably by component distillation or in the presence of dewatering agent (as molecular sieve)) of removing generation.

Can make the intermediate of formula II by the ester of reduction formula III:

Wherein R represents alkyl, preferably ethyl.The general appropriate reductant (as lithium aluminium hydride) of using is carried out this reaction at inert solvent (as tetrahydrofuran (THF)) under-80-20 ℃ temperature.

Can make the compound and the formula CH of formula IV ₂=N-C (R ⁴) (R ⁵) CO ₂R (R wherein ⁴, R ⁵With R as defined above) imine reaction make the ester of formula III:

Wherein, R ¹And R ²As defined above.This reaction is general in the presence of solvent or do not exist under the situation of solvent under the temperature of the boiling point of 90-200 ℃ or solvent and carry out.When the solvent that uses was inert solvent (as dimethylbenzene), preferably the acetone of generation was removed in distillation.

The formula IV compound is known, perhaps can use or adopt known method to make.

Can make above-mentioned formula I compound by the mutual conversion of other formula I compound, this conversion has constituted other characteristics of the present invention.According to another feature of the present invention, can be by being that the sulphur atom of 0 or 1 respective compound carries out oxidation to make n be 1 or 2 compound to n.Generally use 3-chlorine peroxybenzoic acid for example in inert solvent (as methylene dichloride)-40 ℃ of oxidations of carrying out sulphur atom to the temperature of room temperature.

Can use known method that some formula I compound is changed into agricultural acceptable salt.

Following non-limiting examples is used to illustrate the present invention.Except as otherwise noted, otherwise NMR spectrum is at CDCl ₃Middle test obtains.

Embodiment 1

At 20 ℃ with 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2, the dichloromethane solution of 4-dimethyl-3-amylalcohol (1.7g) adds in pyridinium chlorochromate (1.81g) and the stirred mixture of Powdered molecular sieve (4A) in methylene dichloride.After 5 hours, add ether, filter this mixture and evaporate it with hyflo.With dry silica gel column chromatography purifying resistates, use the dichloromethane/ethyl acetate wash-out, obtain 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-propione (compound 1,0.84g) white solid, m.p.98.6-101.6 ℃.Use identical method, can make following compounds:

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-heptanone (compound 2, m.p.75.8-76.6 ℃);

1-(3, the 5-difluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 3), m.p.156.8-157.8 ℃;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 27, m.p.118-119 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-hexanone (compound 29, m.p.118-119 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5-dimethyl-3-hexanone (compound 30, m.p.72-73 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-propione (compound 28, m.p.102-103 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-hendecanone (compound 38), NMR0.8 (t, 3H), 1.2 (m, 10H), 1.4 (s, 6H), 1.6 (q, 2H), 1.85 (s, 3H), 2.4 (t, 2H), 5.15 (s, 2H), 7.25 (m, 5H);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-3-hexanone (compound 32, m.p.84-84.5 ℃);

1-cyclopropyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 31, m.p.126-128 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4,4-trimethylammonium-propione (compound 90, m.p.139-140.5 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(2-thienyl)-1-acetone (compound 91, m.p.152-153.5 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-1-(3-furyl)-2-methyl isophthalic acid-acetone (compound 92, m.p.164-165 ℃);

1-(2-[4-morpholinodithio base)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 93, m.p.169-169.5 ℃);

1-(3, the 4-dichlorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 94, m.p.120-121 ℃);

1-(3, the 5-dichlorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 39, m.p.120.5-121.5 ℃);

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-1-(3, the 5-3,5-dimethylphenyl)-3-methyl-2-butanone (compound 95, m.p.119-120 ℃);

1-(4-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 96, m.p.165.5-166 ℃);

1-cyclopentyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 97, m.p.126-128 ℃);

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl isophthalic acid-(3-aminomethyl phenyl)-2-butanone (compound 98, m.p.97.5-99 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-nonanone (compound 35, m.p.59-60 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-octanone (compound 34, m.p.82-82.5 ℃);

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl isophthalic acid-(phenyl)-2-butanone (compound 99, m.p.117-118 ℃);

1-(3, the 5-difluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 100, m.p.92.5-94 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(6-picoline-2-yl)-1-acetone (compound 101, m.p.76.5-77.5 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6-dimethyl-3-heptanone (compound 102, m.p.83.5-84 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(4-5-flumethiazine-2-yl)-1-acetone (compound 103, m.p.134-135 ℃);

1-(2, the 5-difluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 104, m.p.98-99 ℃);

1-(2-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 105, m.p.140.5-141 ℃);

1-(2,4 difluorobenzene base)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 106, m.p.135-136 ℃);

1-(4-fluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 107, m.p.118-119 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-6-teracrylic acid-ketone (compound 108, m.p.91-92 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-3-heptanone (compound 109), NMR 0.7 (t, 3H), 1.0 (d, 3H), 1.15-1.3 (m, 4H), 1.45 (s, 6H), 1.85 (s, 3H), 2.9 (m, 1H), 5.2 (s, 2H), 7.25 (m, 5H);

2-[2,3-dihydro-5-(2-fluorophenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone (compound 43), NMR 0.9 (t, 3H), 1.25 (m, 2H), 1.45 (s, 6H), 1.6 (q, 2H), 1.9 (s, 3H), 2.5 (t, 2H), 5.3 (s, 2H), 7.1 (m, 2H), 7.3 (m, 2H);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-5-teracrylic acid-ketone (compound 110), and NMR 1.15 (d, 3H), 1.2 (s, 6H), 1.85 (s, 3H), 5.0 (q, 1H), 5.2 (s, 2H), 5.7 (q, 1H), 7.25 (m, 5H);

2-[2,3-dihydro-5-(2-fluorophenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone (compound 111), NMR 0.8 (t, 3H), 1.4 (s, 6H), 1.6 (m, 2H), 1.8 (s, 3H), 2.4 (t, 2H), 5.2 (s, 2H), 7.05 (m, 2H), 7.25 (m, 2H);

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone (compound 112, m.p.87-88.5 ℃);

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone (compound 48, m.p.65-67 ℃);

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-6-teracrylic acid-ketone (compound 113, m.p.62-63 ℃);

1-cyclohexyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone (compound 36, m.p.94-96 ℃);

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone (compound 114, m.p.94 ℃);

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone (compound 56, m.p.75-76 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5-dimethyl-3-heptanone (compound 115, m.p.55-56 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6,6-trimethylammonium-3-heptanone (compound 116, m.p.107.5-109 ℃);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-ethyl-2-methyl-3-hexanone (compound 117), NMR 0.77 (t, 3H), 1.4 (m, 2H), 1.5 (s, 6H), 1.6-1.7 (m, 2H), 1.8 (s, 3H), 2.65 (m, 1H), 5.2 (s, 2H), and 7.1-7.3 (m, 5H);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5,5-trimethylammonium-3-hexanone (compound 118), NMR 0.92 (s, 9H), 1.33 (s, 6H), 2.1 (s, 3H), 2.4 (s, 2H), 5.2 (s, 2H), 7.15-7.3 (m, 5H);

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-6-teracrylic acid-ketone (compound 119, m.p.79-81 ℃);

1-cyclopentyl-2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone (compound 120, m.p.103-104.5 ℃);

1-cyclobutyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 33, m.p.136-137.5 ℃); And 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-7,7,7-three fluoro-3-heptanone (compound 121, m.p.83-84.5 ℃).

Use identical method, do not make following compounds but do not add molecular sieve:

1-(2-fluoro-5-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 4, m.p.113-114.6 ℃);

1-(3-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 5), m.p.134.5-136 ℃; And

1-(3-trifluoromethyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone (compound 6), m.p.105.9-106.9 ℃.

Embodiment 2

At 25 ℃ with chromic acid (1.7ml, the solution of 0.4g sodium dichromate 99 in 1.2ml water is added the solution that forms after being diluted with water to 2ml subsequently in the 0.54ml vitriol oil) drop to the 2-(2 of stirring, 3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-diethyl ether solution of 2-methyl-5-hexene-3-ol (1.0g) in.Separate ether layer after 18 hours, use sodium hydrogen carbonate solution (2N) and salt water washing successively, dried over mgso and evaporation.Resistates is used the methylene dichloride wash-out with dry silica gel column chromatography purifying, obtain yellow oily 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-5-hexene-3-one (compound 7,0.12g), NMR ¹H δ 1.4 (s, 6H), 1.88 (s, 3H), 3.22 (d, 2H), 5.05 (m, 2H), 5.22 (s, 2H), 5.9 (m, 1H), 7.2-7.35 (m, 5H).

Use identical method, make following formula I compound:

4-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene-3-ketone (compound 8, m.p.123-124 ℃);

1-(4-fluorophenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone (compound 9, m.p.92-96 ℃);

The 4-of yellow oily (2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene alkynes-3-ketone (compound 10), NMR ¹H δ 1.45 (s, 6H), 1.9 (s, 3H), 3.05 (s, 1H), 5.25 (s, 2H), 7.2-7.4 (m, 5H);

2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-1-(2-aminomethyl phenyl)-colourless jelly of 2-methyl isophthalic acid-acetone (compound 11), NMR ¹H δ 1.7 (s, 6H), 1.85 (s, 3H), 2.39 (s, 3H), 5.4 (s, 2H), 6.9-7.7 (m, 8H);

The 1-of yellow oily (4-fluoro-3-aminomethyl phenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone (compound 12), NMR ¹H δ 1.6 (s, 6H), 1.85 (s, 3H), 2.2 (s, 3H), 5.4 (s, 2H), 6.85-7.9 (m, 7H);

The 2-of colorless oil (2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(2-aminomethyl phenyl)-1-acetone (compound 13), NMR ¹H δ 1.6 (s, 6H), 1.85 (s, 3H), 2.35 (s, 3H), 5.3 (s, 2H), 6.9 (dd, 2H), 7.05 (t, 1H), 7.1-7.3 (m, 5H), 7.55 (d, 1H);

1-(4-fluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone yellow solid (compound 14), NMR ¹H δ 1.55 (s, 6H), 1.85 (s, 3H), 5.35 (s, 2H), 6.9-7.05 (m, 4H), 7.15-7.25 (m, 3H), 8.0 (dd, 2H); And

1-(4-fluoro-3-aminomethyl phenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone milk yellow solid (compound 15), NMR ¹H δ 1.55 (s, 6H), 1.85 (s, 3H), 2.2 (d, 3H), 5.35 (s, 2H), 6.9 (m, 3H), 7.1-7.3 (m, 3H), 7.75-7.9 (m, 2H).

Embodiment 3

At-60 ℃ the 1.05g oxalyl chloride is added in the stirred mixture of methyl-sulphoxide (1.3g) in methylene dichloride.After 10 minutes, add 1.86g 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-phenyl-1-propyl alcohol, after 0.5 hour, add triethylamine (2.8g) again.Mixture is warmed to room temperature, pour in the water, and wash organic phase with water, use dried over mgso, the evaporation and with silica gel column chromatography purifying resistates, with 5: 1 hexane/ethyl acetate wash-out, obtain 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-phenyl-1-acetone (compound 16, m.p.122-123 ℃).

Make following formula I compound with identical method:

1-(2-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 17, m.p.142-145 ℃);

1-(3-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 18, m.p.134-136 ℃);

1-(4-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 19, m.p.131-132 ℃);

1-(3-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 20, m.p.108-109 ℃); And

1-(3, the 5-dichlorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone (compound 21, m.p.164-167 ℃).

Embodiment 4

Under 0 ℃ of inert atmosphere, in 10 minutes, isopropyl-magnesium chloride (solution of 5ml 2M in tetrahydrofuran (THF)) is added the 2-(2 that stirs, 3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-tetrahydrofuran solution of 2 methyl propanal (2g) in.In 1 hour, mixture is warmed to 10 ℃, be poured in the ammonium chloride saturated solution and with extracted with diethyl ether it.With the dried over mgso organic phase and evaporate it, obtain yellow gelationus 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-3-amylalcohol (2.26g), m.p.42-54 ℃, NMR ¹H δ 0.85 (d, 3H), 0.95 (d, 3H), 1.4 (s, 3H), 1.5 (s, 3H), 1.65 (m, 1H), 1.85 (s, 3H), 3.25 (dd, 1H), 5.0 (d, 1H), 5.1 (d, 1H), 5.25 (d, 1H), 7.15-7.35 (m, 5H).

Use identical method, make following formula I compound:

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-enanthol pale solid, m.p.76-84 ℃;

Buttery 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-5-hexene-3-ol, NMR ¹H δ 1.35 (s, 3H), 1.49 (s, 3H), 1.88 (s, 3H), 1.9-2.2 (m, 2H), 3.65 (dt, 1H), 4.55 (d, 1H), 5.0 (m, 2H), 5.1 (d, 1H), 5.2 (d, 1H), 5.85 (m, 1H), 7.15-7.35 (m, 5H);

The 4-of yellow oily (2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene-3-alcohol, NMR ¹H δ 1.35 (s, 3H), 1.5 (s, 3H), 1.85 (s, 3H), 4.05 (m, 1H), 5.0 (d, 1H), 5.1-5.29 (m, 4H), 5.75 (ddd, 1H), 7.15-7.3 (m, 5H);

The 1-of colorless oil (4-fluorophenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-propyl alcohol, NMR 1.52 (s, 6H), 1.8 (s, 3H), 4.45 (brs, 1H), 4.75 (s, 2H), 4.8 (s, 1H), 6.9-7.4 (m, 8H);

The 4-of yellow oily (2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene alkynes-3-alcohol, NMR ¹H δ 1.5 (s, 3H), 1.55 (s, 3H), 1.85 (s, 3H), 2.35 (s, 1H), 4.35 (dd, 1H), 5.15 (d, 1H), 5.30 (d, 1H), 5.85 (d, 1H), 7.15-7.35 (m, 5H);

The 2-[5-of light yellow oily (2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-1-(2-aminomethyl phenyl)-2-methyl isophthalic acid-propyl alcohol, NMR ¹H δ 1.4 (s, 3H), 1.65 (s, 3H), 1.8 (s, 3H), 2.3 (s, 3H), 4.7 (d, 1H), 4.88 (d, 1H), 5.1 (d, 1H), 7.74 (m, 8H);

The 1-of colorless oil (4-fluoro-3-aminomethyl phenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-propyl alcohol, NMR ¹H δ 1.3 (s, 3H), 1.6 (s, 3H), 1.8 (s, 3H), 2.2 (s, 3H), 4.65 (brs, 1H), 4.75 (s, 1H), 5.15 (s, 2H), 6.8-7.4 (m, 7H);

1-(3, the 5-difluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol white solid, m.p.87.6-89 ℃;

1-(2-fluoro-5-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, NMR ¹H δ 1.4 (s, 3H), 1.75 (s, 3H), 1.9 (s, 3H), 4.55 (d, 1H), 4.9 (d, 1H), 5.1 (d, 1H), 6.98 (d, 1H), 7.12 (t, 1H), 7.28 (dd, 2H), 7.35-7.48 (m, 3H), 7.5-7.6 (m, 1H), 7.7-7.8 (m, 1H);

1-(3-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanols white solid, m.p.116.9-118.1 ℃;

1-(3-trifluoromethyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanols white solid, m.p.67-68.2 ℃;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(2-aminomethyl phenyl)-1-propyl alcohol white solid, NMR ¹H δ 1.3 (s, 3H), 1.55 (s, 3H), 1.7 (s, 3H), 2.3 (s, 3H), 4.7 (d, 1H), 4.88 (d, 1H), 5.1 (d, 1H), 5.55 (d, 1H), 7.0-7.4 (m, 9H);

The 1-of colorless oil (4-fluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, NMR ¹H δ 1.4 (s, 3H), 1.68 (s, 3H), 1.9 (s, 3H), 4.5 (d, 1H), 4.75 (d, 1H), 4.8 (d, 1H), 5.9 (d, 1H), 7.0 (t, 2H), 7.2-7.45 (m, 7H);

The 1-of colorless oil (4-fluoro-3-aminomethyl phenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, NMR ¹H δ 1.35 (s, 3H), 1.6 (s, 3H), 1.7 (s, 3H), 2.2 (s, 3H), 4.45 (d, 1H), 4.68 (d, 1H), 4.75 (d, 1H), 5.78 (d, 1H), 6.88 (t, 1H), 6.95-7.05 (m, 2H), 7.2-7.4 (m, 5H);

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-phenyl-1-propyl alcohol, m.p.150-154 ℃:

1-(2-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen base-5-benzene-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, m.p.141-143 ℃;

1-(3-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, m.p.97-98 ℃;

1-(4-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, m.p.138-139 ℃;

1-(3-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, m.p.107-108 ℃;

1-(3, the 5-dichlorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-propyl alcohol, m.p.141-144 ℃;

Use identical method, also make Q for-CH (OH)-following formula I compound.In following table, " Ph " refers to phenyl; " Me " nail base; " Et " refers to ethyl; " Pr " refers to propyl group; " Bu " refers to butyl.When omitting timestamp down, for example CH=CH2 refers to CH=CH ₂

????R1	??R2	????R3	????R4	????R5	M.p. (℃) or NMR
						????Ph	??Me	????Me	??Me	??Me	????a
????Ph	??Me	????n-Pr	??Me	??Me	??82.5-83.5
						????Ph	??Me	????-CH2CHMe2	??Me	??Me	??91-92
????Ph	??Me	????Et	??Me	??Me	??93-95
						????Ph	??Me	N-octyl	??Me	??Me	??64.5-67
????Ph	??Me	????-CH(Me)CH2Me	??Me	??Me	????b
						????Ph	??Me	Cyclopropyl	??Me	??Me	??64-64.5
????Ph	??Me	????t-Bu	??Me	??Me	??122-123
						????Ph	??Me	3, the 4-Cl2 benzyl	??Me	??Me	??112-113
????Ph	??Me	3, the 5-Cl2 benzyl	??Me	??Me	??100.5-101.5
						????Ph	??Me	3, the 5-Me2 benzyl	??Me	??Me	??108-109
????Ph	??Me	The 4-Cl benzyl	??Me	??Me	??91.5-92.5
						????Ph	??Me	Cyclopentyl	??Me	??Me	??89.5-90
????Ph	??Me	The 3-Me benzyl	??Me	??Me	??108.5-109.5
						????Ph	??Me	N-hexyl	??Me	??Me	??77.5-79

????Ph	??Me	N-pentyl	??Me	??Me	??78.5-79.5
						????Ph	??Me	Benzyl	??Me	??Me	??142-143
????Ph	??Me	3, the 5-F2 benzyl	??Me	??Me	??129-130-5
						????Ph	??Me	????-(CH2)2CHMe2	??Me	??Me	??112-112.5
????Ph	??Me	2, the 5-F2 benzyl	??Me	??Me	??113-114
						????Ph	??Me	The 2-Cl benzyl	??Me	??Me	??94-95.5
????Ph	??Me	2, the 4-F2 benzyl	??Me	??Me	??105.5-106.5
						????Ph	??Me	The 4-F benzyl	??Me	??Me	??76-78
????Ph	??Me	????-(CH2)2CH=CH2	??Me	??Me	??74-75
						????Ph	??Me	??-CH(Me)CH2CH2Me	??Me	??Me	??88.5-90
??2-F?Ph	??Me	????n-Bu	??Me	??Me	??84.5-86
						????Ph	??Me	????-CH2CH=CHMe	??Me	??Me
??2-F?Ph	??Me	????n-Pr	??Me	??Me	????c
						2-OMe-Ph	??Me	????n-Pr	??Me	??Me	????d
2-OMe-Ph	??Me	????n-Bu	??Me	??Me	????e
						2-OMe-Ph	??Me	????-(CH2)2CH=CH2	??Me	??Me	????f
????Ph	??Me	Cyclohexyl	??Me	??Me	??58.5-60
						The 2-thienyl	??Me	????n-Pr	??Me	??Me	??88-89
The 2-thienyl	??Me	????n-Bu	??Me	??Me	??98.5-99
						????Ph	??Me	??-CH2CH(Me)CH2Me	??Me	??Me	????g
????Ph	??Me	????-(CH2)2CMe3	??Me	??Me
						????Ph	??Me	??-CH(CH2Me)CH2Me	??Me	??Me
????Ph	??Me	????-CH2CMe3	??Me	??Me
						The 2-thienyl	??Me	????-(CH2)2CH=CH2	??Me	??Me	??66-69
The 2-thienyl	??Me	Cyclopentyl	??Me	??Me	??81-83
						????Ph	??Me	Cyclobutyl	??Me	??Me	??109.5-110
????Ph	??Me	????-(CH2)3CF3	??Me	??Me	??91-92

1-H?NMR(ppm):

(a) 1.1 (d, 3H), 1.4 (s, 3H), 1.53 (s, 3H), 1.9 (s, 3H), 3.82 (q, 1H), 5.09 (d, 1H), 5.15 and 5.25 (dd, 2H), 7.2-7.4 (m, 5H)

(b)?0．95(m，6H),?1．3(m，3H),?1．4(d，3H),?1．6(d，3H),?1．9(s，3H),?3．4(q，1H),5．0(q，1H)，5．15(d，1H)，5．35(d，1H)，7．35(m，5H)

(c)0．9(t，3H)，1．2(m，2H)，1．35(s，3H)，1．5(s，3H)，1．6(m，2H)，1．9(s，3H)，3．5(t，1H)，4．6(d，1H)，5．1(d，1H)，5．3(d，1H)，7．0-7．3(m，5H)

(d)1．3(s，6H)，1．5(m，2H)，1．9(m，3H)，3．78(s，3H)，4．9-5．2(m，2H)，5．24(s，2H)，6．95(m，2H)，7．25(m，2H)

(e)0．8(m，3H)，1．12(t，3H)，1．1-1．5(m，2H)，1．8(m，3H)，3．4(q，2H)，3．7(s，3H)，4．85(br，1H)，5．1(m，1H)，5．2(m，1H)，6．9(m，2H)，7．2(m，2H)

(f)1．4(s，6H)，1．88(s，3H)，2．35(m，2H)，2．6(m，2H)，3．75(s，3H)，5．0(m，2H)，5．27(s，2H)，5．75-5．9(m，1H)，6．9(m，2H)，7．17(m，1H)，7．25(m，1H)，9．4(s，1H)

(g)0．9(t，1H)，0．9(d，3H)，1．0-1．3(m，4H)，1．4(s，3H)，1．55(s，3H)，1．7(m，1H)，1．9(s，3H)，3．6(d，1H)，5．1(d，1H)，5．3(d，1H)，7．2-7．4(m，5H)

Embodiment 5

Under inert atmosphere, under temperature being remained below 0 ℃ situation, chlorination sec-butyl magnesium solution (solution in the 1.14ml 2M tetrahydrofuran (THF)) is added the 4-(2 that stirs, 3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-tetrahydrofuran solution of 4-methyl-1-pentene-3-ketone (0.5g) in.Add the solution of ethyl acetate and ammonium chloride after 2 hours, organic phase is also evaporated with the salt water washing, and generation 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2, and 6-dimethyl-3-octanone (compound 122,0.48g), NMR 1.55 (s, 3H), 1.6 (s, 3H), 2.1 (s, 3H), 2.5 (s, 1H), 5.2 (m, 3H), 5.6 (d, 1H), 5.8 (q, 1H), 7.25 (m, 5H).

Use identical method to make following compounds:

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-6-heptyne-3-ketone (compound 123), NMR 0.9 (d, 3H), 0.9 (t, 3H), 1.2 (m, 5H), 1.45 (s, 6H), 1.9 (s, 3H), 2.5 (m, 2H), 5.3 (s, 2H), 7.3 (m, 5H).

Embodiment 6

Under inert atmosphere in room temperature in 5 minutes, tetrahydrofuran solution with 4.25ml 1M 2-thienyl lithium adds 2-(2 while stirring, 3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-tetrahydrofuran solution of 2 methyl propanal (1.0g) in.Add hydrochloric acid (2M) and ethyl acetate after 72 hours, organic phase is also evaporated with dried over mgso.Resistates silica gel chromatography purifying, with 3: 1 hexane/ethyl acetate wash-out, with obtain after the hexane development 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-and 2-methyl isophthalic acid-(2-thienyl)-1-propyl alcohol (0.36g), m.p.149-151 ℃.

Use identical method to obtain following compounds:

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-1-(3-furyl)-2-methyl isophthalic acid-propyl alcohol, m.p.132-132.5 ℃;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(6-methyl-2-pyridyl)-1-propyl alcohol, and NMR 1.6 (s, 6H), 1.9 (s, 3H), 2.5 (s, 3H), 4.75 (d, 1H), 5.0 (d, 1H), 5.1 (d, 1H), 5.65 (d, 1H), 7.05 (d, 1H), 7.15 (d, 1H), 7.2-7.4 (m, 5H), 7.55 (t, 1H); With

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(4-trifluoromethyl-2-pyridyl)-1-propyl alcohol, and NMR 1.6 (s, 3H), 1.6 (s, 3H), 1.85 (s, 3H), 4.5 (d, 1H), 4.95 (d, 1H), 5.1 (d, 1H), 6.2 (d, 1H), 7.1 (d, 1H), 7.2-7.4 (m, 5H), 7.7 (s, 1H), 8.7 (d, 1H).

Reference example 1

While stirring the tetrahydrofuran solution of 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2 Methylpropionic acid ethyl ester (43g) is added in the lithium aluminium hydride (220ml 1M diethyl ether solution) at-40 ℃.After 1 hour solution is cooled to-70 ℃, with ether dilution and dropping salt solution it is handled, initial temperature is-70 ℃ during processing, and temperature subsequently is-30 ℃.After it is warmed to room temperature, organic layer dried over mgso, evaporation, resistates is used the methylene dichloride wash-out with dry silica gel column chromatography purifying, obtains 2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2 methyl propanal milk yellow solid (22.5g), NMR ¹H δ 1.35 (s, 6H), 1.95 (s, 3H), 5.25 (s, 2H), 7.22-7.38 (m, 5H), 9.42 (s, 1H).

Use identical method to make following compounds:

The 2-[5-of white solid state (2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2 methyl propanal, NMR ¹H δ 1.38 (s, 6H), 1.93 (s, 3H), 4.29 (s, 2H), 7.74 (m, 4H), 9.42 (s, 1H);

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2 methyl propanal, NMR 1.38 (s, 6H), 2.12 (s, 3H), 5.22 (s, 2H), 7.0 (m, 2H), 7.3 (m, 1H), 9.42 (s, 1H); With

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2 methyl propanal, NMR 1.35 (s, 6H), 1.85 (s, 3H), 3.8 (s, 3H), 5.25 (s, 2H), 6.9-7.3 (m, 4H), 9.4 (s, 1H).

Reference example 2

With 5-(2-fluorophenyl)-2,2-dimethyl-6-methyl-4H-1,3-dioxine (dioxin)-4-ketone (2.0g) and 2-(N-methene amido)-2 Methylpropionic acid ethyl ester (1.45g) mixture reflux 10 hours in dimethylbenzene.Resistates is used the cyclohexane/ethyl acetate wash-out with dry silica gel column chromatography purifying after the evaporation drying, obtains [the 5-(2-fluorophenyl)-2 of light yellow oily, 3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2 Methylpropionic acid ethyl ester (1.7g), NMR 1.24 (t, 3H), 1.42 (s, 6H), 1.57 (s, 3H), 4.15 (q, 2H), 5.3 (s, 2H), 7.74 (m, 4H).

Make following compounds with identical method: (2,3-dihydro-6-methyl-4-oxygen base-4H-1,3-oxazine-3-yl)-2 Methylpropionic acid ethyl ester, NMR 1.2 (t, 3H), 1.5 (s, 6H), 1.98 (s, 3H), 2.25 (m, 1H), 4.15 (q, 2H), 5.16 (s, 2H).

Reference example 3

In reflux, in 1 hour, the xylene solution of 2-(N-methene amido)-2 Methylpropionic acid ethyl ester (10.3g) is added in the xylene solution of 2-(2-p-methoxy-phenyl) methyl aceto acetate (8.51g).The reinforced speed of control equals the speed of component distillation (by Dean and Stark separator).Add the diformazan benzo subsequently again and continue distillation 3 hours.Evaporating mixture obtains 2-[2 in a vacuum, 3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-1,3-oxazine-3-yl]-2 Methylpropionic acid ethyl ester (14.1g), and NMR 1.25 (t, 3H), 1.55 (s, 6H), 1.8 (s, 3H), 3.75 (s, 3H), 4.15 (m, 2H), 5.3 (s, 2H), and 6.9-7.3 (m, 4H).

Reference example 4

At 70 ℃ with 2-p-methoxy-phenyl ethyl acetate (11.6g), tert.-butoxy sodium (12.7g) and the mixture heating up of ethyl acetate (15.8g) in diisopropyl ether 2.5 hours, and in stirred overnight at room temperature.Add ethyl acetate and hydrochloric acid (2M), organic phase is also evaporated with dried over mgso.Resistates distills in a vacuum, obtains 2-(2-p-methoxy-phenyl) methyl aceto acetate liquid (8.5g), NMR 1.15 and 1.13 (t, 3H), 1.8 and 2.2 (s, 3H), 3.75 and 3.85 (s, 3H), 4.1-4.3 (2q, 2H), 5.15 (s, 1H), 6.9-7.3 (m, 4H), 13.1 (s, 1H).

Reference example 5

At 50 ℃ with 2-(2,3-dihydro-5-iodo-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl)-2 Methylpropionic acid ethyl ester (30.0g), 2-(tributyl stannyl) thiophene (33.5ml), chlorination two (triphenylphosphine) closed palladium (3.08g) and the mixture heating up of lithium chloride (20.5g) in tetrahydrofuran (THF) 24 hours.Add 2-(tributyl stannyl) thiophene (2.8ml) again and again with this mixture heating up 18 hours.Add chlorination two (triphenylphosphine) and closed palladium (0.62g) and reheat 18 hours.Mixture is poured in the water, used extracted with diethyl ether, organic phase is with the salt water washing, with dried over mgso and evaporation.With obtaining (2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl)-2 Methylpropionic acid ethyl ester (14.5g) behind the silica gel chromatography purifying, NMR1.15 (t, 3H), 1.55 (s, 6H), 2.1 (s, 3H), 4.15 (q, 2H), 5.25 (s, 2H), 6.9-7.4 (m, 3H).

Reference example 6

N-iodine succinimide (238g) is added in the acetic acid solution of 2-(2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-the yl)-2 Methylpropionic acid ethyl ester (200g) that stirs.This mixture was stirred 5 hours at 40-45 ℃, subsequently in stirred overnight at room temperature and evaporate it.Resistates dilutes with ether, and water, sodium carbonate solution (2M) and salt water washing successively is with dried over mgso and evaporate it.The solution of resistates in ethanol is cooled to-40 ℃, obtains 2-(2,3-dihydro-5-iodo-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl)-2 Methylpropionic acid ethyl ester (66.9g), m.p.85-87 ℃.

According to another characteristics of the present invention, the invention provides the composition that is applicable to weeding, it comprises 1 of one or more formula I, 3-oxazine-4-ketone derivatives or its agricultural acceptable salt and one or more are compatible agricultural acceptable diluent or carrier and/or tensio-active agent with it, described formula I compound preferably is evenly dispersed in described one or more and (that is to say, but type that it is generally acknowledged this diluent or carrier and/or tensio-active agent in the art is applicable to herbicidal composition and they and formula I compound compatibility) with it in compatible agricultural acceptable diluent or carrier and/or the tensio-active agent.Term " disperses " to refer to that composition Chinese style I compound dissolution is in other component equably.Term " herbicidal composition " broadly not only comprises to be prepared to be used for the composition of weeding, and comprises the enriched material that uses preceding necessary dilution.Be preferably, composition contains one or more formula I compounds of 0.05-90 weight %.

Herbicidal composition can contain diluent or carrier and tensio-active agent (as moistening, dispersion or emulsification) simultaneously.That can be present in tensio-active agent in the herbicidal composition of the present invention and can be ionic or non-ionic type, sulfonation ricinoleate for example, quaternary ammonium derivative, the condensation product of oxyethane and alkyl and polyaryl phenol (as nonyl or octyl phenol), perhaps sorbitan carboxylic ester, this carboxylicesters by with oxyethane, the condensation of the basic metal of the basic metal of sulfuric ester and sulfonic acid and alkaline earth salt (as sodium sulfosuccinate ester in two ninth of the ten Heavenly Stems and dioctyl ester) and high molecular sulfonic acid and alkaline earth salt (as sodium lignosulfonate and calcium and sodium alkyl benzene sulfonate and calcium) makes the free hydroxyl etherificate and has solvability.

Be preferably, herbicidal composition of the present invention contains the tensio-active agent of 10 weight % (as 0.05-10 weight %) at most, but if necessary, herbicidal composition of the present invention can contain the more tensio-active agent of volume (as contain 15 weight % at most in the emulsible suspending concentrate of liquid state, containing 25 weight % at most in liquid water-soluble concentrate).

The suitable solid diluent or the example of carrier are pure aluminium silicate, fine silica, talcum powder, chalk, magnesia calcined, diatomite, calcium phosphate, dust cork, absorption carbon black and clay such as kaolin and wilkinite.Solids composition (powdery, particulate state or wettable powder powder) is preferably by grinding formula I compound with solid diluent, the solution of formula I compound in volatile solvent is infiltrated in solid diluent or the carrier, boil off solvent subsequently, but and if necessary grinding product make to obtain powder.Granular preparation can (be dissolved in the suitable solvent by making formula I compound, if necessary, this solvent is volatile) be adsorbed in granular solid diluent or the carrier, and can boil off solvent if necessary and make, perhaps by the powder granulation that obtains is above made.In solid herbicidal composition, particularly in wettable powder and particle, can contain wetting agent and dispersion agent (wetting agent of type as described above and dispersion agent), this reagent also plays diluent or carrier when solid-state.

Liquid composition of the present invention can be the aqueous solution, organic or water-organic solution, suspension and the emulsion that is mixed with tensio-active agent.The suitable liquid diluent that adds in the liquid composition comprises water, glycol, glycol ether, tetrahydrofurfuryl alcohol, phenyl methyl ketone, pimelinketone, isophorone, N-alkyl pyrrolidone, toluene, dimethylbenzene, mineral, the rudimentary fragrance of the vegetables oil of animal and plant oil, esterification and oil and naphthalene cut (with the mixture of these thinners).Can be present in tensio-active agent in the liquid composition and can be ionic or non-ionic (tensio-active agent of type as described above) when its during for liquid, also play diluent or carrier.

Powder, dispersible granules and the liquid composition of used water or other suitable diluent (as mineral oil or vegetables oil, be under the situation of liquid concentrate of oil at diluent or carrier especially) dilution enriched material shape, the formation composition is standby.

If necessary, can use the liquid composition of the formula I compound of self-emulsifying enriched material shape, this enriched material contains and is dissolved in the emulsifying agent, or be dissolved in contain emulsifying agent and with the compatible solvent of active substance in active substance, can simply this enriched material be added in the entry, it is standby to form composition.

Can use electrostatic spray technology not diluted directly to use the liquid concentrate of diluent or carrier as oil.

If necessary, herbicidal composition of the present invention also can contain conventional auxiliary agent such as tackiness agent, protective colloid, thickening material, permeate agent, spreading agent, stablizer, intercalating agent, anti-hard caking agent, tinting material and sanitas.These auxiliary agents also play carrier or thinner.

Except as otherwise noted, otherwise following percentage ratio is weight percentage.The present invention's herbicidal composition preferably is:

The waterborne suspension enriched material that comprises one or more formula I compounds of 10-70%, 2-10% tensio-active agent, 0.1-5% thickening material and 15-87.9% water;

The wettable powder that comprises one or more formula I compounds of 10-90%, 2-10% tensio-active agent and 8-88 solid diluent or carrier;

Water-soluble or the water dispersible pow-ders that comprises one or more formula I compounds of 10-90%, 2-40% yellow soda ash and 0-88% solid diluent;

Comprise solvent (as the triethylene glycol) that one or more formula I compounds of 5-50% (as 10-30%), 0-25% tensio-active agent and 10-90% (as 45-85%) can be miscible with water or can with the liquid water-soluble enriched material of the mixture of miscible solvent of water and water;

The liquid emulsible suspension-concentrates that comprises one or more formula I compounds of 10-70%, 5-15% tensio-active agent, 0.1-5% thickening material and 10-84.9% organic solvent (as mineral oil);

Contain one or more formula I compounds of 1-90% (as 25-75%), 1-15% (as 2-10%) tensio-active agent and 5-95% (as 20-60%) solid diluent (as clay), add water and make these components form slurry, the water dispersible particle that the subsequent drying granulation forms; And

Comprise the emulsifiable concentrate of one or more formula I compounds of 0.05-90 (preferably 1-60%), 0.01-10% (preferably 1-10%) tensio-active agent and 9.99-99.94% (preferably 39-98.99%) organic solvent.

Herbicidal composition of the present invention also can contain formula I compound and one or more other have insecticidal activity compound, and if necessary, also can contain acceptable diluent or carrier, tensio-active agent and conventional auxiliary agent recited above with the Pesticidal compound compatibility, and formula I compound is evenly dispersed in preferably in the described compound and diluent or carrier, tensio-active agent and conventional auxiliary agent with insecticidal activity.

Can add or comprise with other example that the herbicidal composition of the present invention that contains weedicide uses with compound of insecticidal activity, for example be used to increase span of control to the weeds kind, as alachlor [2-chloro-2,6 '-diethyl N-(methoxymethyl)-monoacetylaniline], atrazine [2-chloro-4-ethylamino-6-sec.-propyl amino-1,3,5-triazine], bromoxynil [3,5-two bromo-4-hydroxy benzonitriles], chlorotoluron [N '-(3-chloro-4-aminomethyl phenyl)-N, N-dimethyl urea], bladex [2-chloro-4-(1-cyano group-1-methylethyl amino)-6-ethylamino-1,3,5-triazine], 2,4-D[2,4-dichlorophenoxyacetic acid], dicamba 98 [3,6-two chloro-O-Anisic Acids], two benzene azoles fast [1,2-dimethyl-3,5-diphenylpypazole salt], wheat straw volt [N-2-(N-benzoyl-3-chloro-4-fluoroanilino)-methyl propionate], fluometuron [N '-(3-trifluoromethyl)-N, N-dimethyl urea], isoproturon [N '-(4-isopropyl phenyl) N, N-dimethyl urea], diclofop-methyl (RS)-2-[4-(2, the 4-dichlorophenoxy) phenoxy group] propionic acid } oxazole diclofop-methyl is with Gao oxazole diclofop-methyl { 2-[4-(6-chloro-1,3-benzoxazole-2-oxygen base) phenoxy group] propionic acid }, { N-(2 for diflufenican, the 4-difluorophenyl)-2-[3-(trifluoromethyl) phenoxy group]-the 3-picolinamide }, tralkoxydim 2-[1-(ethoxy imino) propyl group]-3-hydroxyl-5-(2,4, the 6-trimethylphenyl)-the 2-cyclopentenone }, clodinafop{2-[4-(5-chloro-3-fluoro-2-pyridyloxy) phenoxy group] propionic acid }, sulcotrione[2-(2-chloro-4-methyl sulphonyl benzoyl) hexanaphthene-1,3-diketone], flurtamone 5-methylamino-2-phenyl-4-[3-(trifluoromethyl) phenyl]-3-(2H)-furanone }, aclonifen (2-chloro-6-nitro-3-phenoxybenzamine) and alkylsulfonyl urea are as nicoculsfuron; Insecticide such as synthetic pyrethroid (as permethrin and Cypermethrin); and sterilant such as carbamate are (as N-(1-butyl-formamyl benzimidazolyl-2 radicals-yl) Urethylane) and triazole (as 1-(4-chloro-phenoxy group)-3; 3-dimethyl-1-(1; 2, the 4-triazol-1-yl)-2-butanone).

If necessary, the acid compound with insecticidal activity that can add in the herbicidal composition of the present invention or therewith use or other biological activity acid material (for example above-mentioned compound in front) can use its conventional derivative, as an alkali metal salt and amine salt and ester.

Another characteristics according to the present invention provide a kind of goods, it comprises 1 of at least a formula I, 3-oxazine-4-ketone derivatives, perhaps preferably include foregoing herbicidal composition, the weeding enriched material that must dilute before better being to use, comprise 1 of at least a formula I at goods described in the container that is used for above-mentioned one or more formula I derivatives or described herbicidal composition, 3-oxazine-4-ketone derivatives, and point out that with the explanation that described container directly links to each other one or more formula I derivatives or the herbicidal composition that are contained are used to control weed growth.Described container is that to be generally used for being stored in envrionment temperature be solid chemical and herbicidal composition, the sort of container of the herbicidal composition of enriched material shape particularly, metal or plastics pot or tube, glass and Plastic Bottle as interior lacquering, and (when the material in the container is solid, during as granular herbicidal composition) box, as carton box, plastics and can or sack.Described container has enough volumes usually, so that hold 1, the amount of 3-oxazine-4-ketone derivatives or herbicidal composition is enough to handle at least one acre of soil, controlling the weed growth in this soil, is volume easily but be no more than working method for routine.Explanation can directly link to each other with this container (as directly being printed thereon, or being printed on the label or card that is fixed thereon).The material (if necessary after diluting) that this explanation indicates in the container usually is used to control the growths of weeds with the amount of application of per hectare 0.5-5000g active substance with foregoing method, to reach foregoing purpose.

The following example is used to illustrate herbicidal composition of the present invention.In description, use following trade mark: Ethylan, Soprophor, Sopropo, Rhodorsil, Atagel, Synperonic, Solvesso, Arkopon, Tixosil.

Embodiment C 1

Make suspending concentrate: oxazinone derivative (chemical compounds I) 20%Ethylan BCP (tensio-active agent) 0.5%Soprophor FL 0.5%Sopropon T36 (dispersion agent) 0.2%Rhodorsil 426R (defoamer) 0.01% propylene glycol (frostproofer) 5.0%Atagel 50 (antisettling agents) 2.0 water to 100% with following component

Qi Ta oxazinone derivative of Yong replaces chemical compounds I to make similar suspending concentrate.

Embodiment C 2

Make emulsification enriched material: oxazinone derivative with following component, (chemical compounds I) 10%Synperonic NPE1800, (tensio-active agent) 4.9%Arylan CA, (tensio-active agent) 5.0% pimelinketone, (solvent) 9.8%NMP, (solvent) 9.8%Solvesso 150, (dopant) 5.0% water to 100%

Annotate: NMP is meant N-Methyl pyrrolidone

Qi Ta oxazinone derivative of Yong replaces chemical compounds I to make similar emulsification enriched material.

Embodiment C 3

Make wettable powder: oxazinone derivative (chemical compounds I) 20.0%Arylan SX sheet (tensio-active agent) 3.0%Arkopon T (tensio-active agent) 5.0% poly carboxylic acid sodium (dispersion agent) 1.0%Tixosil 38 (flow promotor) 3.0% china clay 68.0% with following component

Qi Ta oxazinone derivative of Yong replaces chemical compounds I to make similar wettable powder.

The invention provides a kind of method in place control weeds (being nonconforming plant) growth, it comprises formula I 1 from least a herbicidally effective amount to this place that use, and 3-oxazine-4-ketone derivatives or its agricultural go up acceptable salt.For reaching this purpose, such as will be described, described 1,3-oxazine-4-ketone derivatives comes into operation with the form of herbicidal composition (promptly and be applicable to using with its compatible diluent or carrier and/or tensio-active agent in the herbicidal composition) usually.

When using before bud and/or behind the bud, formula I compound shows the weeding activity to dicotyledonous (being broad-leaved) and unifacial leaf (i.e. grass) weeds.Specifically, this compound has activity for optionally control barnyard grass (Echinochloa crus-galli) in the rice field.

Term " is used before the bud " and is referred to stretch out the soil application weedicide that the soil surface forward direction exists weed seed or seedling in weeds.Term " is used behind the bud " and is pointed to the aerial or extension of the weeds stretch out soil surface and use weedicide.For example formula I compound can be used for controlling the growth of following weeds:

Broadleaf weeds, as piemarker, Amaranthus retroflexus, three leaf thorn grass, lamb's-quarters, Tender Catchweed Bedstraw Herb, Ipomoea Pharbitis purpurea, Sesbania exaltata, wild Europe sinapsis alba, black nightshade and Noogoora burr, and

Gramineous weeds (grass weeds), as mouse tail amur foxtail, wild avena sativa, lady's-grass, barnyard grass, yard grass and Setaria spp such as Fa Shi dog hair grass or Herba Setariae Viridis, and

Reed such as tiger nuts.

The amount of application of formula I compound is with performance different and different of the characteristic of weeds, employed composition, time of application, weather and edaphic condition and (when the growths of control weeds in the plant growth district) crop.When being applied to the plant growth district, amount of application should be able to be enough to control the growth of weeds and crop do not caused permanent damage substantially.Consider these factors, the amount of application of per hectare 1-1000g active substance generally can obtain good result.The particular problem that is run into when however, it should be understood that according to the control weeds can be used higher or lower amount of application.

Can be before crop sowing or after planting, before perhaps crop germinates or the back of germinateing in direct or non-direct mode (as direct or non-direct spraying) with before the compound bud or the after-applied place of spreading to weeds of bud, the growth of use formula I compound selective ground control weeds (as controlling the weeds of kind noted earlier), described place is to be used for maybe will being used to grow that (such as grain is as wheat for crop, barley, oat, corn and rice, soybean, broad bean, dwarf bean, pea, clover, cotton, peanut, flax, onion, Radix Dauci Sativae, Caulis et Folium Brassicae capitatae, rape (oilseed rape), Sunflower Receptacle, beet and grassland permanent or sowing).Optionally control weeds for the place that the weeds the crop (crop as previously described) that is used for maybe will being used to growing spread, the active substance amount of application that is preferably per hectare is 10-500g, is preferably 25-250g.

The compounds of this invention is specially adapted to control gramineous weeds.

Also can be by with before the formula I compound bud of the present invention or be applied to the orchard built up and other arboreal growth district (as forest, the woods and park) and plantation (as sugar cane plantation, oil palm plantation and rubber plantation) growth behind the bud with control weeds, particularly above-mentioned weeds.In order to reach this purpose, can be before or after plantation trees or construction plantation, can occur in the soil of weeds to weeds or expection in the mode (as direct spraying or spraying indirectly) of directly using or using indirectly, with per hectare 50-5000g, be preferably 50-2000g, the amount that is preferably 100-1000g applies active substance.

Formula I compound also is used in non-plant growth district, but the growth of the weeds of place the control weeds, particularly mentioned kind of needs control weeds.

The example in this non-plant growth district comprises airport, manufacturing district, railway, roadside, river bank, irrigation advance and other current next door, jungle and slack season ground or unreclaimed soil, particularly need to control the growth of weeds to reduce the place of fire hazard.When being used for the purpose of the complete herbicidal effect of this normal needs, the application dosage of active compound often is higher than foregoing application dosage in the plant growth district.Dosage depends on plant characteristic to be processed and desired treatment effect accurately.

For reaching this this purpose, be preferably with direct or non-direct mode (as direct or non-direct spraying) with per hectare 50-5000g, be preferably 50-2000g, be preferably before the amount bud of active substance of 100-1000g or use behind the bud, preferably use before the bud.

When use before the bud with control weeds growth the time, formula I compound can be sneaked in the soil that weeds can occur.Use formula I compound after also can bud with control weed growth (promptly being applied to the aerial or exposed portions serve of germination weeds), this up-to-date style I compound generally also can contact with soil, and also can play control action kou before the bud to the weeds that germinate in back in the soil.

If necessary, can repeat to apply formula I compound to the place that needs the long-term control weeds.

The using method of herbicidal composition:

Test method (A)

A) universal method

The compound dissolution that plant is handled in an amount of being used for forms the solution that is equivalent to the maximum 1000g amount of application of per hectare test compound (g/ha) at acetone.Laboratory weeding atomizer with standard applies these solution, and spray amount is equivalent to 290 liters of spraying liquids of per hectare.

B) weeds control: before the bud

With planting seed at 70mm ², the grain weight of the every basin of in the fertile soil in the dark plastic tub of 75mm. is as follows: about amount 1 in the every basin of weeds kind) broad leaved weed piemarker 10 Amaranthus retroflexus 20 clearvers 10 garden leaves 10 wild Europe sinapsis albas, 15 Noogoora burrs 22 of leading a cow) grassy weed mouse tail amur foxtail 15 wild oats 10 barnyard grasses 15 green bristlegrass 203) reed chufa 3 crops 1) broad leaf crop cotton 3 soybean 32) gramineous crop corn 2 rice 6 wheats 6

As described in (a), The compounds of this invention is applied to the soil surface that contains seed.Basin to various crops and various weeds carries out a kind of processing, and with group in contrast spraying and that only do not spray with acetone.

After treatment, these basins are placed put into the glass canopy on the kapillary mat, and water from top.Spray and with the naked eye estimate the infringement of crop after 20-24 days.The result compares with the plant in the contrast basin, represents with the percentage ratio of crop or weed growth decline or infringement.

C) weeds control: behind the bud

Weeds and crop are directly sowed, 70mm dark at 75mm ²Basin in John Innes basin carry in the mixed fertilizer, but Amaranthus retroflexus the seedling stage the spraying last week extract and transplant to basin.Till plant being grown to be used to the compound of handling these plants to be sprayed in brooder.Plant quantity is as follows in every basin:

1) the every basin plant of broad leaved weed weeds kind is counted growth phase piemarker 3 1-2 leaf Amaranthus retroflexus 4 1-2 leaf clearvers 3 first round (whorl) garden leaves 3 1-2 Ye Ye Europe sinapsis albas, 42 leaf Noogoora burrs, the 1 2-3 leaf 2 of leading a cow) in the every basin of grassy weed plant count growth phase mouse tail amur foxtail 8-12 1-2 leaf wild oat 12-18 1-2 leaf barnyard grass 4 2-3 leaf green bristlegrass 15-25 1-2 leaves 3) in the every basin of reed plant count growth phase chufa 33 leaves 1) in the every basin of broad leaf crop crop plant count growth phase cotton 21 leaf soybean 22 leaves 2) the every basin plant of gramineous crop crop counts growth phase corn 2 2-3 leaf rice 4 2-3 leaf wheats 5 2-3 leaves

Plant as described in being applied to as the compound that will be used to handle plant as described in (a).Basin to various crops and various weeds carries out a kind of processing, and with group in contrast spraying and that only do not spray with acetone.

After treatment, these basins are placed put into the glass canopy on the kapillary mat, and watered once from top in per 24 hours and carry out controlled sub-irrigation subsequently.Spray and with the naked eye estimate crop damage and weeds control after 20-24 days.The result compares with the plant in the contrast basin, represents with the percentage ratio of crop or weed growth decline or infringement.

Test method (B)

A) universal method

Identical with top test method A, but solution applied with antomobile sprayer, and spray amount is equivalent to 720 liters of spraying liquids of per hectare.

B) weeds control: before the bud

With planting seed at 70mm ², the grain weight of the every basin of in the fertile soil in the dark plastic tub of 75mm.3 kinds of every basin kinds. is as follows: about grain weight 1 in the every basin of weeds kind) broad leaved weed piemarker 7-8 Amaranthus retroflexus 20 (pugil) clearvers 4-5 garden leaf 5 wild Europe sinapsis alba 7-8 Xinjiang Tripleurospermum limosum 20 (pugil) chickweeds, 20 (pugil) 2 of leading a cow) grassy weed mouse tail amur foxtail 15-20 wild oat 10 barnyard grasses 15 green bristlegrass 15 Fa Shi dog hairs grass (Setaria faberii) 15 Ah draping over one's shoulders draw grass (Apera spica-venti) 20 (pugil) crop 1) and broad leaf crop cotton 3 soybean 22) gramineous crop corn 2 rice 5 wheats 5

As described in (a), The compounds of this invention is applied to the soil surface that contains seed.The a plurality of basins that contain described type seed are carried out a kind of processing, and with group in contrast spraying and that only do not spray with acetone.

After treatment, these basins are placed put into the glass canopy on the kapillary mat, and water from top.Spray and with the naked eye estimate the infringement of crop after 17 days.The result compares with the plant in the contrast basin, represents with the percentage ratio of crop or weed growth decline or infringement.

Test method C

Use behind the bud to rice in brooder

Paddy soil is inserted 170cm ²Plastic tub in, add an amount of water and chemical fertilizer, it is kneaded into the rice field state.

Rice seedlings (the kind: Koshihikari) transplant to each basin every basin two strains in 2 leaf stages will be grown in brooder.In each basin, sow rice field barnyard grass (Echinochloaoryzicola), Sheathed Monochoria, Procumbent Falsepimpernel and firefly Lin's of predetermined amount seed subsequently respectively, and it is dark to add water to 3cm.

In brooder, plant growing to rice field barnyard grass was reached for 1.5 leaf stages, use the described compound of embodiment to make solution, make in the solution that the content of activeconstituents is 75,300 and 1200g/ha with 100% acetone.Drip this solution with dropper.

Apply compound after 21 days, with the naked eye estimate to the herbicidal effects of various weeds and to the phytotoxicity of rice seedlings, the plant in result and the contrast basin relatively descends with the growths of crop or weeds or the percentage ratio of infringement is represented.

In test method A, when applying 1000g/ha or less amount before the bud, The compounds of this invention 1-6,9-21,27-36,38,39,43,56,90-111,114-116,118-123 can make the growth of one or more above-mentioned weeds descend 80% at least; Weeds are had toxic applying under the dosage, these compounds have selectivity at least a crop.

In test method B, when applying 1000g/ha before the bud or still less the time, The compounds of this invention 7 and 8 can make the growth of one or more above-mentioned weeds descend 90% at least.

In test method A, in the time of as the after-applied 1000g/ha of bud or still less, The compounds of this invention 1,2,5,6,15,16 and 18 can make the growth of one or more above-mentioned weeds descend 80% at least; To having under the toxic dosage, these compounds have selectivity to a kind of crop at least.In test method C, when applying 1200g/ha or still less the time, The compounds of this invention 1-10.13-21,6,39,43,48,56,90,91,93-100,102,104-109,111-11416-123 can make the growth of one or more above-mentioned weeds descend 80% at least.

Claims (18)

1. 1 of a formula I, 3-oxazine-4-ketone derivatives or its agricultural go up acceptable salt:

Wherein, R ¹The phenyl that expression can be replaced arbitrarily by 1-5 group, described group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁷,-CO ₂R ⁷,-COR ⁷, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁷And phenoxy group;

5-7 unit hetero-aromatic ring with 1-4 heterocyclic atom, described heterocyclic atom can be identical or different, be selected from nitrogen, oxygen and sulphur, described heterocycle at random by 1-4 identical or different be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁷,-CO ₂R ⁷,-COR ⁷, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁷Replace with the group of phenoxy group;

Or contain 10 carbon atoms and at random halogenated straight or branched alkyl, alkenyl or alkynyl at most;

R ²Representative:

Hydrogen atom; Or

Have 1-10 carbon atom, at random by one or more identical or different R ⁸The straight or branched alkyl that group replaced;

Be up to 10 carbon atoms also at random by halogenated straight or branched alkenyl or alkynyl;

Or be selected from cyano group ,-CHO ,-COR ⁷,-CO ₂H ,-CO ₂R ⁷,-COSR ⁷,-CONR ⁹R ¹⁰,-CH=NOH ,-CH=NOR ⁷,-CH=NOCOR ⁷,-CH=NNR ⁹R ¹⁰,-CH ₂CN ,-CH ₂NO ₂Group with Oxyranyle;

R ³Representative-(CH ₂) _r-(phenyl or naphthyl that is replaced by 1-5 group at random, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶, phenoxy group and-SF ₅);

-(CH ₂) _s-(5-7 unit hetero-aromatic ring with 1-4 heterocyclic atom, described heterocyclic atom can be identical or different, be selected from nitrogen, oxygen and sulphur, described heterocycle can at random condense with phenyl ring, perhaps condense with second 5-7 unit hetero-aromatic ring with 1-4 identical or different heterocyclic atom that is selected from nitrogen, oxygen and sulphur, form two member ring systems, any one ring in monocycle or two member ring systems can at random be replaced by 1-4 group, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶And phenoxy group);

Be up to 10 carbon atoms and can at random halogenated straight or branched alkyl, alkenyl or alkynyl;

Be up to 10 carbon atoms, halogenation at random and straight or branched alkyl, alkenyl or alkynyl with cycloalkyl substituted of 3-6 carbon atom; Perhaps

Have the cycloalkyl of 3-6 carbon atom or have the cycloalkenyl group of 5-6 carbon atom, their ring can be at random by identical or different R ⁶Group or one or more halogen atom replace;

R ⁴And R ⁵Represent low alkyl group respectively;

R ⁶And R ⁷Represent low alkyl group or low-grade halogenated alkyl respectively;

N represents 0,1 or 2;

Q represents 1 or 2;

R represents 0,1 or 2; S represents 0 or 1;

R ⁸Be halogen ,-OH ,-OR ⁷,-OCOR ⁷,-S (O) _nR ⁷,-NR ⁹R ¹⁰Or trinitride;

R ⁹And R ¹⁰Represent hydrogen, low alkyl group or low-grade halogenated alkyl respectively;

Q representative-C (=O)-,-CH (OH)-or-C (OR ¹¹) (OR ¹¹)-; R wherein ¹¹Represent low alkyl group; Perhaps two-OR ¹¹Group forms 5 yuan or 6 yuan of ring ketal groups with the carbon atom that they connected.

2. 1 of formula I as claimed in claim 1,3-oxazine-4-ketone derivatives or its agricultural go up acceptable salt, wherein:

R ¹The phenyl that expression can be replaced arbitrarily by 1-5 group, described group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁷,-CO ₂R ⁷,-COR ⁷, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁷And phenoxy group; Or

5-7 unit hetero-aromatic ring with 1-4 heterocyclic atom, described heterocyclic atom can be identical or different, be selected from nitrogen, oxygen and sulphur, described heterocycle at random by 1-4 identical or different be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁷,-CO ₂R ⁷,-COR ⁷, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁷Replace with the group of phenoxy group;

Or contain 10 carbon atoms and at random halogenated straight or branched alkyl, alkenyl or alkynyl at most;

R ²Representative:

Hydrogen atom; Or

Have 1-10 carbon atom, at random by one or more identical or different R ⁸The straight or branched alkyl that group replaced;

Be up to 10 carbon atoms also at random by halogenated straight or branched alkenyl or alkynyl;

Or be selected from cyano group ,-CHO ,-COR ⁷,-CO ₂H ,-CO ₂R ⁷,-COSR ⁷,-CONR ⁹R ¹⁰,-CH=NOH ,-CH=NOR ⁷,-CH=NOCOR ⁷,-CH=NNR ⁹R ¹⁰,-CH ₂CN ,-CH ₂NO ₂Group with Oxyranyle;

R ³Representative-(CH ₂) _r-(phenyl that is replaced by 1-5 group at random, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶And phenoxy group);

-(CH ₂) _s-(5-7 unit hetero-aromatic ring with 1-4 heterocyclic atom, described heterocyclic atom can be identical or different, be selected from nitrogen, oxygen and sulphur, described heterocycle can at random condense with phenyl ring, perhaps condense with second 5-7 unit hetero-aromatic ring with 1-4 identical or different heterocyclic atom that is selected from nitrogen, oxygen and sulphur, form two member ring systems, any one ring in monocycle or two member ring systems can at random be replaced by 1-4 group, described substituting group can be identical or different, be selected from halogen, hydroxyl, low alkyl group, low-grade halogenated alkyl, lower alkoxy, elementary halogenated alkoxy ,-S (O) _nR ⁶,-CO ₂R ⁶,-COR ⁶, cyano group, nitro ,-O (CH ₂) _qCO ₂R ⁶And phenoxy group); Perhaps

Be up to 10 carbon atoms and can at random halogenated straight or branched alkyl, alkenyl or alkynyl; Or

Cycloalkyl with 3-6 carbon atom, it can be at random by identical or different R ⁶Group or one or more halogen atom replace;

R ⁴And R ⁵Represent low alkyl group respectively;

R ⁶And R ⁷Represent low alkyl group or low-grade halogenated alkyl respectively;

N represents 0,1 or 2;

Q represents 1 or 2;

R represents 0 or 1; S represents 0 or 1;

R ⁸Be be selected from halogen ,-OH ,-OR ⁷,-OCOR ⁷,-S (O) _nR ⁷With-NR ⁹R ¹⁰Group;

R ⁹And R ¹⁰Represent hydrogen, low alkyl group or low-grade halogenated alkyl respectively;

Q representative-C (=O)-,-CH (OH)-or-C (OR ¹¹) (OR ¹¹)-; R wherein ¹¹Represent low alkyl group; Perhaps two-OR ¹¹Group forms 5 yuan or 6 yuan of ring ketal groups with the carbon atom that they connected.

3. compound as claimed in claim 1 or 2, wherein R ¹Representative is at random by one or more phenyl that group replaced or thienyls that are selected from halogen, low alkyl group and low-grade halogenated alkyl.

4. compound as claimed in claim 3, wherein R ¹Represent phenyl.

5. as any one described compound, wherein R among the claim 1-4 ²Representative has the straight or branched alkyl of 1-6 carbon atom.

6. compound as claimed in claim 5, wherein R ²Represent methylidene.

7. as any one described compound, wherein R among the claim 1-6 ⁴And R ⁵The difference represent methylidene.

8. as any one described compound among the claim 1-7, wherein Q representative-C (=O)-.

9. as any one described compound, wherein R among the claim 1-8 ³Represent cyclopentyl.

10. as any one described compound, wherein R among the claim 1-8 ³Represent normal-butyl or butenyl.

11. compound as claimed in claim 1 or 2, wherein R ¹The phenyl that representative is at random replaced by halogen;

R ², R ⁴And R ⁵The difference represent methylidene;

Q representative-C (=O)-;

R ³Representative-(CH ₂) _r-(at random be selected from halogen and have 1 or 2 carbon atom and can be) at random by the phenyl that group replaced of halogenated alkyl by one or two;

Or be up to straight or branched alkyl, the alkenyl or alkynyl of 4 carbon atoms;

R is 0 or 1.

12. compound as claimed in claim 1 or 2, wherein:

R ¹Representative is at random by halogen or methyl substituted phenyl or thienyl;

R ², R ⁴And R ⁵The difference represent methylidene;

Q representative-C (=O)-;

R ³Representative-(CH ₂) _r-(phenyl that at random is selected from halogen or has 1 or 2 carbon atoms and can at random be replaced) by the group of halogenated alkyl by 1 or 2;

Be up to the straight or branched alkyl or alkenyl of 6 carbon atoms;

Or has a cycloalkyl of 3-6 carbon atom;

R is 0 or 1.

13. compound as claimed in claim 1, it has one or more following features:

R ¹Representative is at random by the phenyl or the thienyl of halogen or methoxyl group replacement;

R ², R ⁴And R ⁵The difference represent methylidene;

Q representative-C (=O)-;

R ³Representative-(CH ₂) _r-(at random by 1 or 2 phenyl that is selected from the group replacement of halogen or methyl);

At random by thienyl, furyl, benzothiazolyl or pyridyl that halogen or any halogenated methyl replaced;

Being up to 8 carbon atoms also can be at random by halogenated straight or branched alkyl, alkenyl or alkynyl;

Or has a cycloalkyl of 3-6 carbon atom;

R is 0 or 1.

14. compound as claimed in claim 1, it is:

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-propione;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-heptanone;

1-(3, the 5-difluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(2-fluoro-5-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(3-trifluoromethyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-5-hexene-3-one;

4-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene-3-ketone;

1-(4-fluorophenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone;

4-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-methyl-1-pentene alkynes-3-ketone;

2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-1-(2-aminomethyl phenyl)-2-methyl isophthalic acid-acetone;

1-(4-fluoro-3-aminomethyl phenyl)-2-[5-(2-fluorophenyl)-2,3-dihydro-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(2-aminomethyl phenyl)-1-acetone;

1-(4-fluorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(4-fluoro-3-aminomethyl phenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-phenyl-1-acetone;

1-(2-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(4-chloro-phenyl-)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3-trifluoromethyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone; Or

1-(3, the 5-dichlorophenyl)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-hexanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5-dimethyl-3-hexanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-propione;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-hendecanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-3-hexanone;

1-cyclopropyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4,4-trimethylammonium-propione;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(2-thienyl)-1-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-1-(3-furyl)-2-methyl isophthalic acid-acetone;

1-(2-[4-morpholinodithio base)-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

1-(3, the 4-dichlorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(3, the 5-dichlorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-1-(3, the 5-3,5-dimethylphenyl)-3-methyl-2-butanone;

1-(4-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-cyclopentyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-prop-1-acetone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl isophthalic acid-(3-aminomethyl phenyl)-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-nonanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-3-octanone;

3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl isophthalic acid-(phenyl)-2-butanone;

1-(3, the 5-difluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(6-picoline-2-yl)-1-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6-dimethyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-(4-5-flumethiazine-2-yl)-1-acetone;

1-(2, the 5-difluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(2-chloro-phenyl-)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(2,4 difluorobenzene base)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

1-(4-fluorophenyl)-3-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-3-methyl-2-butanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-6-teracrylic acid-ketone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,4-dimethyl-3-heptanone;

2-[2,3-dihydro-5-(2-fluorophenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-5-teracrylic acid-ketone;

2-[2,3-dihydro-5-(2-fluorophenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone;

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone;

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone;

2-[2,3-dihydro-5-(2-p-methoxy-phenyl)-6-methyl-4-oxygen-4H-1,3-oxazine-3-yl]-2-methyl-6-teracrylic acid-ketone;

1-cyclohexyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-3-hexanone;

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone;

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5-dimethyl-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6,6-trimethylammonium-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-4-ethyl-2-methyl-3-hexanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,5,5-trimethylammonium-3-hexanone;

2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl-6-teracrylic acid-ketone;

1-cyclopentyl-2-[2,3-dihydro-6-methyl-4-oxygen-5-(2-thienyl)-4H-1,3-oxazine-3-yl]-2-methyl isophthalic acid-acetone;

1-cyclobutyl-2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl isophthalic acid-acetone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-7,7,7-three fluoro-3-heptanone;

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2,6-dimethyl-3-octanone; Perhaps

2-(2,3-dihydro-6-methyl-4-oxygen-5-phenyl-4H-1,3-oxazine-3-yl)-2-methyl-6-heptyne-3-ketone.

15. a herbicidal composition, it comprise significant quantity as any one is described 1 among the claim 1-14,3-oxazine-4-ketone derivatives or its agricultural go up acceptable salt, and agricultural goes up acceptable diluent or carrier and/or tensio-active agent.

16. in place control method for weed, it comprise to this place apply significant quantity as claim 1-14 in any one described 1,3-oxazine-4-ketone derivatives or its agricultural go up acceptable salt, perhaps apply herbicidal composition as claimed in claim 15.

17. method as claimed in claim 16 is characterized in that described place is the zone that is used for maybe will being used for kind of plant, and 1, the amount that the 3-oxazine-the 4-ketone derivatives is applied is 0.001-1.0kg/ha.

18. a formula I 1 as claimed in claim 1 or 2, the preparation method of 3-oxazine-4-ketone derivatives, it comprises:

(a) when Q representative-C (=O)-time, oxidation Q representative-CH (OH)-the respective compound of formula I;

(b) when Q representative-CH (OH)-time, make the aldehyde and the formula R of formula II ³The organometallic compound reaction of-M:

Wherein, R ¹, R ², R ⁴And R ⁵As claim 1 or 2 definition, R ³As claim 1 or 2 definition, M represents metal group;

(c) as Q representative-C (OR ¹¹) (OR ¹¹)-time, make Q representative-C (=O)-the respective compound and the formula R of formula I ¹¹The alcohol reaction of-OH, wherein R ¹¹Such as claim 1 definition; Perhaps

(d) when n is 1 or 2, oxidation n is the sulphur atom of the respective compound of 0 or 1 formula I;

The formula I compound that randomly will so obtain changes into its agricultural and goes up acceptable salt.